Ion exchange system for lithium extraction

ABSTRACT

The present invention relates to the extraction of lithium from liquid resources such as natural and synthetic brines, leachate solutions from clays and minerals, and recycled products.

CROSS-REFERENCE

This application claims the benefit of U.S. Provisional ApplicationsNos. 62/540,511, filed Aug. 2, 2017, and 62/582,208, filed Nov. 6, 2017,which applications are incorporated herein by reference in theirentireties.

BACKGROUND OF THE INVENTION

Lithium is an essential element for high-energy rechargeable batteriesand other technologies. Lithium can be found in a variety of liquidsolutions, including natural and synthetic brines and leachate solutionsfrom minerals and recycled products

SUMMARY OF THE INVENTION

Lithium can be extracted from liquid resources using an ion exchangeprocess based on inorganic ion exchange materials. Inorganic ionexchange materials absorb lithium ions from a liquid resource whilereleasing hydrogen ions, and then elute lithium ions in acid whileabsorbing hydrogen ions. The ion exchange process can be repeated toextract lithium ions from a liquid resource and yield a concentratedlithium ion solution. The concentrated lithium ion solution can befurther processed into chemicals for the battery industry or otherindustries.

An aspect described herein is a system for the extraction of lithiumions from a liquid resource, comprising: a) an ion exchange material;and b) a pH modulating setup for increasing the pH of the liquidresource in the system.

In some embodiments, the ion exchange material is loaded in a vessel. Insome embodiments, the ion exchange material is loaded in a plurality ofvessels. In some embodiments, the pH modulating setup is connected tothe vessel loaded with the ion exchange material. In some embodiments,the vessel further comprises a plurality of injection ports, wherein theplurality of injection ports is used to increase the pH of the liquidresource in the system. In some embodiments, the pH modulating setupfurther comprises one or more tanks.

In some embodiments, the pH modulating setup is a tank comprising: a)one or more compartments; and b) a means for moving the liquid resourcethrough the one or more compartments. In some embodiments, the ionexchange material is loaded in at least one compartment. In someembodiments, the tank further comprises a means for circulating theliquid resource throughout the tank. In some embodiments, the means forcirculating the liquid resource throughout the tank is a mixing device.In some embodiments, the tank further comprises an injection port.

An aspect described herein is a system for the extraction of lithiumions from a liquid resource, comprising a tank, wherein the tank furthercomprises: a) one or more compartments; b) an ion exchange material; c)a mixing device; and d) a pH modulating setup for changing the pH of thesystem, wherein the ion exchange material is used to extract lithiumions from the liquid resource.

In some embodiments, the ion exchange material is loaded in at least oneof the one or more compartments. In some embodiments, the pH modulatingsetup comprises a pH measuring device and an inlet for adding base. Insome embodiments, the pH measuring device is a pH probe. In someembodiments, the inlet is an injection port. In some embodiments, thetank further comprises a porous partition. In some embodiments, theporous partition is a porous polymer partition.

An aspect described herein is a system for the extraction of lithiumions from a liquid resource comprising an ion exchange material and aplurality of columns, wherein each of the plurality of columns isconfigured to transport the ion exchange material along the length ofthe column and the ion exchange material is used to extract lithium ionsfrom the liquid resource.

In some embodiments, at least one of the plurality of columns comprisesan acidic solution. In some embodiments, at least one of the pluralityof columns comprises the liquid resource. In some embodiments, each ofthe plurality of columns is configured to transport the ion exchangematerial by a pipe system or an internal conveyer system.

In some embodiments, the ion exchange material comprises a plurality ofion exchange particles. In some embodiments, the plurality of ionexchange particles in the ion exchange material is selected fromuncoated ion exchange particles, coated ion exchange particles andcombinations thereof. In some embodiments, the ion exchange material isa porous ion exchange material. In some embodiments, the porous ionexchange material comprises a network of pores that allows liquids tomove quickly from the surface of the porous ion exchange material to theplurality of ion exchange particles. In some embodiments, the ionexchange material is in the form of porous ion exchange beads. In someembodiments, the liquid resource is a natural brine, a dissolved saltflat, seawater, concentrated seawater, a desalination effluent, aconcentrated brine, a processed brine, an oilfield brine, a liquid froman ion exchange process, a liquid from a solvent extraction process, asynthetic brine, a leachate from an ore or combination of ores, aleachate from a mineral or combination of minerals, a leachate from aclay or combination of clays, a leachate from recycled products, aleachate from recycled materials, or combinations thereof.

An aspect described herein is a device for lithium extraction from aliquid resource comprising one or more vessels independently configuredto simultaneously accommodate porous ion exchange beads moving in onedirection and alternately acid, brine, and optionally other solutionsmoving in the net opposite direction.

In some embodiments, at least one of the one or more vessels are fittedwith a conveyer system suitably outfitted to move porous ion exchangebeads upward and simultaneously allow a net flow of acid, brine, andoptionally other solutions, downward. In some embodiments, the porousion exchange beads comprise ion exchange particles that reversiblyexchange lithium and hydrogen and a structural matrix material, andhaving a pore network. In some embodiments, the liquid resourcecomprises a natural brine, a dissolve salt flat, a concentrated brine, aprocessed brine, a filtered brine, a liquid from an ion exchangeprocess, a liquid from a solvent extraction process, a synthetic brine,leachate from ores, leachate from minerals, leachate from clays,leachate from recycled products, leachate from recycled materials, orcombinations thereof.

An aspect described herein is a method of extracting lithium ions from aliquid resource, comprising: a) flowing the liquid resource through asystem described herein to produce a lithiated ion exchange material;and b) treating the lithiated ion exchange material from a) with an acidsolution to produce a salt solution comprising lithium ions.

An aspect described herein is a method of extracting lithium ions from aliquid resource, comprising: a) flowing the liquid resource through thetank of a system described herein to produce a lithiated ion exchangematerial; and b) treating the lithiated ion exchange material from a)with an acid solution to produce a salt solution comprising lithiumions.

An aspect described herein is a method of extracting lithium ions from aliquid resource, comprising: a) flowing the liquid resource into asystem comprising a tank to produce a lithiated ion exchange material,wherein the tank further comprises (i) one or more compartments, (ii) anion exchange material, (iii) a mixing device, and (iv) a pH modulatingsetup for changing the pH of the liquid resource; and b) treating thelithiated ion exchange material from a) with an acid solution to producea hydrogen-rich ion exchange material and a salt solution comprisinglithium ions. In some embodiments, the method further comprises prior tob), washing the lithiated ion exchange material with an aqueoussolution. In some embodiments, the method further comprises subsequentto b), washing the hydrogen-rich ion exchange material with an aqueoussolution. In some embodiments, the pH modulating setup comprises a pHmeasuring device and an inlet for adding base. In some embodiments, thepH measuring device is a pH probe. In some embodiments, the inlet is apipe. In some embodiments, the inlet is an injection port. In someembodiments, the method further comprises, during a), the pH modulatingsetup measuring a change in pH. In some embodiments, the change in pHtriggers the addition of a base to maintain lithium uptake. In someembodiments, the change in pH to below a pH value of about 2 to about 9triggers the addition of base to maintain lithium uptake.

In some embodiments of the methods described herein, the tank furthercomprises a porous partition. In some embodiments, the porous partitionis a porous polymer partition.

An aspect described herein is a method of extracting lithium ions from aliquid resource, comprising: a) providing a system comprising an ionexchange material, a tank comprising one or more compartments; and amixing device, wherein (i) the ion exchange material is oxide-based andexchanges hydrogen ions with lithium ions, and (ii) the mixing device iscapable of moving the liquid resource around the tank comprising one ormore compartments; b) flowing the liquid resource into the system of a)thereby contacting the liquid resource with the ion exchange material,wherein the ion exchange material exchanges hydrogen ions with lithiumions in the liquid resource to produce lithiated ion exchange material;c) removing the liquid resource from the system of b); d) flowing anacid solution into the system of c) thereby contacting the acid solutionwith the lithiated ion exchange material, wherein the lithiated ionexchange material exchanges lithium ions with the hydrogen ions in theacid solution to produce the ion exchange material and a salt solutioncomprising lithium ions from the lithiated ion exchange material; and e)collecting the salt solution comprising the lithium ions for furtherprocessing.

In some embodiments of the methods described herein, the liquid resourceis a natural brine, a dissolved salt flat, seawater, concentratedseawater, a desalination effluent, a concentrated brine, a processedbrine, an oilfield brine, a liquid from an ion exchange process, aliquid from a solvent extraction process, a synthetic brine, a leachatefrom an ore or combination of ores, a leachate from a mineral orcombination of minerals, a leachate from a clay or combination of clays,a leachate from recycled products, a leachate from recycled materials,or combinations thereof.

In some embodiments of the methods described herein, the acid solutioncomprises hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromicacid, chloric acid, perchloric acid, nitric acid, formic acid, aceticacid, or combinations thereof.

An aspect described herein is a process for lithium extraction from aliquid resource comprising treating ion exchange material alternatelywith acid, brine, and optionally other solutions, in a configurationwhere the material moves in the net opposite direction to the acid,brine, and optionally other solutions, thereby producing alithium-enriched solution from the liquid resource.

In some embodiments of the process for lithium extraction from a liquidresource, the process comprises: a) treating the ion exchange materialwith acid under conditions suitable to absorb hydrogen to generatehydrogen-enriched material and release lithium to generate alithium-enriched solution; b) optionally, washing the hydrogen-enrichedmaterial with water to generate hydrogen-enriched material substantiallyfree of residual acid; c) treating the hydrogen-enriched material withthe liquid resource under conditions suitable to absorb lithium togenerate lithium-enriched material; d) optionally, washing thelithium-enriched material with water to generate lithium-enrichedmaterial substantially free of liquid resource; and e) repeating thecycle to produce a lithium-enriched solution from the liquid resource.In some embodiments, the ion exchange material comprises ion exchangeparticles that reversibly exchange lithium and hydrogen and a structuralmatrix material, and having a pore network. In some embodiments of theprocesses described herein, the liquid resource comprises a naturalbrine, a dissolved salt flat, a concentrated brine, a processed brine, afiltered brine, a liquid from an ion exchange process, a liquid from asolvent extraction process, a synthetic brine, leachate from ores,leachate from minerals, leachate from clays, leachate from recycledproducts, leachate from recycled materials, or combinations thereof.

An aspect described herein is a process for the extraction of lithiumions from a liquid resource, comprising: a) contacting an ion exchangematerial with the liquid resource; and b) increasing the pH of theliquid resource before contact with the ion exchange material, duringcontact with the ion exchange material, after contact with the ionexchange material, or combinations thereof. In some embodiments, the ionexchange material is loaded into one or more compartments in a tank. Insome embodiments, the process further comprises moving the liquidresource through the one or more compartments in the tank. In someembodiments, the tank comprises injection ports. In some embodiments,the process further comprises using the injection ports to increase thepH of the liquid resource before contact with the ion exchange material,during contact with the ion exchange material, after contact with theion exchange material, or combinations thereof. In some embodiments, theion exchange material is loaded into one or more vessels. In someembodiments, the one or more vessels further comprise a plurality ofinjection ports. In some embodiments, the process further comprisesusing the plurality of injection ports to increase the pH of the liquidresource before contact with the ion exchange material, during contactwith the ion exchange material, after contact with the ion exchangematerial, or combinations thereof.

In some embodiments of the processes described herein, the ion exchangematerial comprises a plurality of ion exchange particles. In someembodiments, the plurality of ion exchange particles in the ion exchangematerial is selected from uncoated ion exchange particles, coated ionexchange particles and combinations thereof. In some embodiments, theion exchange material is a porous ion exchange material. In someembodiments, the porous ion exchange material comprises a network ofpores that allows liquids to move quickly from the surface of the porousion exchange material to the plurality of ion exchange particles. Insome embodiments, the porous ion exchange material is in the form ofporous ion exchange beads.

INCORPORATION BY REFERENCE

All publications, patents, and patent applications mentioned in thisspecification are herein incorporated by reference to the same extent asif each individual publication, patent, or patent application wasspecifically and individually indicated to be incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

The novel features of the invention are set forth with particularity inthe appended claims. A better understanding of the features andadvantages of the present invention will be obtained by reference to thefollowing detailed description that sets forth illustrative embodiments,in which the principles of the invention are utilized, and theaccompanying drawings of which:

FIG. 1 illustrates a recirculating batch system comprising an ionexchange column, a mixing tank, a settling tank, and a recirculationtank.

FIG. 2 illustrates a recirculating batch system comprising an ionexchange column, a mixing tank, and a recirculation tank.

FIG. 3 illustrates a column interchange system comprising a brinecircuit, a water washing circuit, and an acid circuit.

FIG. 4 illustrates a column interchange system comprising a brinecircuit, a water washing circuit, and an acid recirculation loop.

FIG. 5 illustrates a stirred tank system comprising a tank, a basemixing tank, and a permeable compartment for holding ion exchange beads.

FIG. 6 illustrates a ported ion exchange column system comprising an ionexchange column with multiple ports along the length of the column forinjection of base.

FIG. 7 illustrates a coated ion exchange particle.

FIG. 8 illustrates a porous ion exchange bead.

FIG. 9 illustrates an ion exchange column with a moving bed of beadsthat move in an opposite direction of flows of brine, acid, and othersolutions.

FIG. 10 illustrates the assembly of an acid column and a brine column,which move ion exchange beads in opposite directions of liquid flows.

FIG. 11 illustrates the assembly of an acid column, a water washingcolumn, a brine column, and another water washing column.

FIG. 12 illustrates the assembly of various acid, brine, and waterwashing columns with various flow rates of liquid solutions and beads,various column heights, and various bead and brine residence times.

FIG. 13 illustrates an escalator system with a conveyer belt with finsattached to the conveyer belt.

FIG. 14 illustrates an escalator system with a sliding surface that isfixed in position and fins that are attached to a separate conveyersystem.

FIG. 15 illustrates a porous bead containing ion exchange particles,matrix material, and pores formed by removing filler material.

FIG. 16 illustrates a stirred tank reactor with a pH modulating setup.

FIG. 17 illustrates a stirred tank reactor with a pH modulating setupand a compartment for containing ion exchange particles.

FIG. 18 illustrates a pair of stirred tank reactors including a largestirred tank reactor with a pH modulating setup and a small stirred tankreactor.

FIG. 19 illustrates a network of stirred tank reactors with acontinuously operated circuit for a liquid resource.

FIG. 20 illustrates a network of stirred tank reactors that each operatein batch mode and operate together in a switched network.

DETAILED DESCRIPTION OF THE INVENTION

The terms “lithium”, “lithium ion”, and “Li⁺” are used interchangeablyin the present specification and these terms are synonymous unlessspecifically noted to the contrary. The terms “hydrogen”, “hydrogenion”, “proton”, and “H⁺” are used interchangeably in the presentspecification and these terms are synonymous unless specifically notedto the contrary.

As used herein, the words “column” and “vessel” are usedinterchangeably. In some embodiments described herein referring to a“vessel”, the vessel is a column. In some embodiments described hereinreferring to a “column”, the column is a vessel.

The term “the pH of the system” or “the pH of” a component of a system,for example one or more tanks, vessels, columns, pH modulating setups,or pipes used to establish fluid communication between one or moretanks, vessels, columns, or pH modulating setups, refers to the pH ofthe liquid medium contained or present in the system, or contained orpresent in one or more components thereof. In some embodiments, theliquid medium contained in the system, or one or more componentsthereof, is a liquid resource. In some embodiments, the liquid mediumcontained in the system, or one or more components thereof, is a brine.In some embodiments, the liquid medium contained in the system, or oneor more components thereof, is an acid solution, an aqueous solution, awash solution, a salt solution, a salt solution comprising lithium ions,or a lithium-enriched solution.

Lithium is an essential element for batteries and other technologies.Lithium is found in a variety of liquid resources, including natural andsynthetic brines and leachate solutions from minerals, clays, andrecycled products. Lithium is optionally extracted from such liquidresources using an ion exchange process based on inorganic ion exchangematerials. These inorganic ion exchange materials absorb lithium from aliquid resource while releasing hydrogen, and then elute lithium in acidwhile absorbing hydrogen. This ion exchange process is optionallyrepeated to extract lithium from a liquid resource and yield aconcentrated lithium solution. The concentrated lithium solution isoptionally further processed into chemicals for the battery industry orother industries.

Ion exchange materials are optionally formed into beads and the beadsare optionally loaded into ion exchange columns for lithium extraction.Alternating flows of brine, acid, and other solutions are optionallyflowed through an ion exchange column to extract lithium from the brineand produce a lithium concentrate, which is eluted from the column usingthe acid. As brine flows through the ion exchange column, the beadsabsorb lithium while releasing hydrogen, where both the lithium andhydrogen are cations. The release of hydrogen during lithium uptake willacidify the brine and limit lithium uptake unless the pH of the brine isoptionally maintained in a suitable range to facilitatethermodynamically favorable lithium uptake and concomitant hydrogenrelease.

To control the pH of the brine and maintain the pH in a range that issuitable for lithium uptake in an ion exchange column, bases such asNaOH, Ca(OH)₂, CaO, KOH, or NH₃ are optionally added to the brine assolids, aqueous solutions, or in other forms. For brines that containdivalent ions such as Mg, Ca, Sr, or Ba, addition of base to the brinecan cause precipitation of solids, such as Mg(OH)₂ or Ca(OH)₂, which cancause problems for the ion exchange reaction. These precipitates causeproblems in at least three ways. First, precipitation can remove basefrom solution, leaving less base available in solution to neutralizeprotons and maintain pH in a suitable range for lithium uptake in theion exchange column. Second, precipitates that form due to base additioncan clog the ion exchange column, including clogging the surfaces andpores of ion exchange beads and the voids between ion exchange beads.This clogging can prevent lithium from entering the beads and beingabsorbed by the ion exchange material. The clogging can also cause largepressure heads in the column. Third, precipitates in the column dissolveduring acid elution and thereby contaminate the lithium concentrateproduced by the ion exchange system. For ion exchange beads to absorblithium from brine, an ideal pH range for the brine is optionally 6 to9, a preferred pH range is optionally 4 to 9, and an acceptable pH rangeis optionally 2 to 9.

System of Modulating pH for the Extraction of Lithium

An aspect of the invention described herein is an ion exchange reactorfor lithium extraction with a form that allows for pH control duringlithium uptake from a brine or other lithium ion-containing liquidresource. This reactor functions to neutralize hydrogen that is releasedduring lithium uptake, while solving the problems associated withprecipitation from base addition.

An aspect of the invention described herein is a system for theextraction of lithium ions from a liquid resource, comprising: a) an ionexchange material; and b) a pH modulating setup for increasing pH of theliquid resource in the system. The ion exchange material extractslithium ions from a liquid resource. During the extraction of lithiumions from a liquid resource by the ion exchange material, the pH of theliquid resource optionally decreases. Increasing the pH of the liquidresource in the system by using a pH modulating setup maintains the pHin a range that is suitable for lithium ion uptake by the ion exchangematerial. In an embodiment, the pH modulating setup comprises measuringthe pH of the system and adjusting the pH of the system to an ideal pHrange for lithium extraction. In an embodiment, for ion exchangematerial to absorb lithium from brine, an ideal pH range for the brineis optionally 6 to 9, a preferred pH range is optionally 4 to 9, and anacceptable pH range is optionally 2 to 9. In an embodiment, the pHmodulating setup comprises measuring the pH of the system and whereinthe pH of the system is less than 6, less than 4, or less than 2, the pHof the system is adjusted to a pH of 2 to 9, a pH of 4 to 9, or a pH of6 to 9.

Recirculating Batch System

In an embodiment of the system, the ion exchange material is loaded in acolumn. In an embodiment of the system, the pH modulating setup isconnected to the column loaded with the ion exchange material. In anembodiment of the system, the pH modulating setup comprises one or moretanks.

In some embodiments of the systems described herein, the ion exchangematerial is loaded in a vessel. In some embodiments, the pH modulatingsetup is in fluid communication with the vessel loaded with the ionexchange material. In some embodiments, the pH modulating setup is influid communication with the column loaded with the ion exchangematerial.

In one embodiment of the system, one or more ion exchange columns areloaded with a fixed or fluidized bed of ion exchange beads. In oneembodiment of the system, the ion exchange column is a cylindricalconstruct with entry and exit ports. In a further embodiment, the ionexchange column is optionally a non-cylindrical construct with entry andexit ports. In a further embodiment, the ion exchange column optionallyhas entry and exit ports for brine pumping, and additional doors orhatches for loading and unloading ion exchange beads to and from thecolumn. In a further embodiment, the ion exchange column is optionallyequipped with one or more security devices to decrease the risk of theftof the ion exchange beads. In one embodiment, these beads contain ionexchange material that can reversibly absorb lithium from brine andrelease lithium in acid. In one embodiment, the ion exchange material iscomprised of particles that are optionally protected with coatingmaterial such as SiO₂, ZrO₂, or TiO₂ to limit dissolution or degradationof the ion exchange material. In one embodiment, these beads contain astructural component such as an acid-resistant polymer that binds theion exchange materials. In one embodiment, the beads contain pores thatfacilitate penetration of brine, acid, aqueous, and other solutions intothe beads to deliver lithium and hydrogen to and from the bead or towash the bead. In one embodiment, the bead pores are structured to forma connected network of pores with a distribution of pore sizes and arestructured by incorporating filler materials during bead formation andlater removing that filler material in a liquid or gas.

In one embodiment of the system, the system is a recirculating batchsystem, which comprises an ion exchange column that is connected to oneor more tanks for mixing base into the brine, settling out anyprecipitates following base addition, and storing the brine prior toreinjection into the ion exchange column or the other tanks. In oneembodiment of the recirculating batch system, the brine is loaded intoone or more tanks, pumped through the ion exchange column, pumpedthrough a series of tanks, and then returned to the ion exchange columnin a loop. In one embodiment, the brine optionally traverses this looprepeatedly. In one embodiment, the brine is recirculated through the ionexchange column to enable optimal lithium uptake by the beads. In oneembodiment, base is added to the brine in such a way that pH ismaintained at an adequate level for lithium uptake and in such a waythat the amount of base-related precipitates in the ion exchange columnis minimized.

In one embodiment, as the brine is pumped through the recirculatingbatch system, the brine pH drops in the ion exchange column due tohydrogen release from the ion exchange beads during lithium uptake, andthe brine pH is adjusted upward by the addition of base as a solid,aqueous solution, or other form. In one embodiment, the ion exchangesystem drives the ion exchange reaction to near completion, and the pHof the brine leaving the ion exchange column approaches the pH of thebrine entering the ion exchange column. In one embodiment, the amount ofbase added is optionally controlled to neutralize the hydrogen releasedby the ion exchange beads in such a way that no basic precipitates form.In one embodiment, an excess of base or a transient excess of base isoptionally added in such a way that basic precipitates form. In oneembodiment, the basic precipitates form transiently and then areredissolved partially or fully by the hydrogen that is released from theion exchange column. In one embodiment of the system, base is optionallyadded to the brine flow prior to the ion exchange column, after the ionexchange column, prior to one or more tanks, or after one or more tanks.

In one embodiment of the recirculating batch system, the tanks include amixing tank where the base is mixed with the brine. In one embodiment,the tanks include a settling tank, where precipitates such as Mg(OH)₂optionally settle to the bottom of the settling tank to avoid injectionof the precipitates into the ion exchange column. In one embodiment, thetanks include a storage tank where the brine is stored prior toreinjection into the ion exchange column, mixing tank, settling tank, orother tanks. In one embodiment, the tanks include an acid recirculationtank. In one embodiment, some tanks in the recirculating batch reactoroptionally serve a combination of purposes including base mixing tank,settling tank, acid recirculation tank, or storage tank. In anyembodiment, a tank optionally does not fulfil two functions at the sametime. For example, a tank is not a base mixing tank and a settling tank.

In one embodiment of the recirculating batch system, base is added to amixing tank, which is optionally a continuous stirred tank system, aconfluence of acidified brine flow and base flow followed by a staticmixer, a confluence of acidified brine flow and base flow followed by apaddle mixer, a confluence of acidified brine flow and base flowfollowed by a turbine impeller mixer, or a continuous stirred tanksystem in the shape of a vertical column which is well mixed at thebottom and settled near the top. In one embodiment, the base isoptionally added as a solid or as an aqueous solution. In oneembodiment, the base is optionally added continuously at a constant orvariable rate. In one embodiment, the base is optionally addeddiscretely in constant or variable aliquots or batches. In oneembodiment, the base is optionally added according to one or more pHmeters, which optionally samples brine downstream of the ion exchangecolumn or elsewhere in the recirculating batch system. In oneembodiment, filters are optionally used to prevent precipitates fromleaving the mixing tank. In one embodiment, the filters are optionallyplastic mesh screens, small packed columns containing granular mediasuch as sand, silica, or alumina, small packed columns containing porousmedia filter, or a membrane.

In one embodiment of the recirculating batch system, the settling tankis optionally a settling tank with influent at bottom and effluent attop or a settling tank with influent on one end and effluent on anotherend. In one embodiment, chambered weirs are used to fully settleprecipitates before brine is recirculated into reactor. In oneembodiment, solid base precipitates are collected at the bottom of thesettling tank and recirculated into the mixer. In one embodiment,precipitates such as Mg(OH)₂ optionally settle near the bottom of thetank. In one embodiment, brine is removed from the top of the settlingtank, where the amount of suspended precipitates is minimal. In oneembodiment, the precipitates optionally settle under forces such asgravity, centrifugal action, or other forces. In one embodiment, filtersare optionally used to prevent precipitates from leaving the settlingtank. In one embodiment, the filters are optionally plastic meshscreens, small packed columns containing granular media such as sand,silica, or alumina, small packed columns containing porous media filter,or a membrane. In one embodiment, baffles are optionally used to ensuresettling of the precipitate and to prevent the precipitate from exitingthe settling tank and entering the column.

In one embodiment of the recirculating batch system, basic precipitatesare optionally collected from the settling tank and reinjected into thebrine in a mixing tank or elsewhere to adjust the pH of the brine.

In one embodiment of the recirculating batch system, one or more ionexchange columns are optionally connected to one or more tanks or set oftanks. In one embodiment of the recirculating batch system, there areoptionally multiple ion exchange columns recirculating brine through ashared set of mixing, settling, and storage tanks. In one embodiment ofthe recirculating batch system, there is optionally one ion exchangecolumn recirculating brine through multiple sets of mixing, settling,and storage tanks.

Column Interchange System

An aspect of the invention described herein is a system wherein the ionexchange material is loaded in a plurality of columns. In an embodiment,the pH modulating setup comprises a plurality of tanks connected to theplurality of columns, wherein each of the plurality of tanks isimmediately connected to one of the plurality of columns. In anembodiment, two or more of the plurality of tanks connected to theplurality of columns forms at least one circuit. In an embodiment, threeor more of the plurality of tanks connected to the plurality of columnsforms at least two circuits. In an embodiment, three or more of theplurality of tanks connected to the plurality of columns forms at leastthree circuits. In an embodiment, at least one circuit is a liquidresource circuit. In an embodiment, at least one circuit is a waterwashing circuit. In an embodiment, at least one circuit is an acidsolution circuit. In an embodiment, at least two circuits are waterwashing circuits.

In one embodiment of the ion exchange system, the system is a columninterchange system where a series of ion exchange columns are connectedto form a brine circuit, an acid circuit, a water washing circuit, andoptionally other circuits. In one embodiment of the brine circuit, brineflows through a first column in the brine circuit, then into a nextcolumn in the brine circuit, and so on, such that lithium is removedfrom the brine as the brine flows through one or more columns. In oneembodiment of the brine circuit, base is added to the brine before orafter each ion exchange column or certain ion exchange columns in thebrine circuit to maintain the pH of the brine in a suitable range forlithium uptake by the ion exchange beads. In one embodiment of the acidcircuit, acid flows through a first column in the acid circuit, theninto the next column in the acid circuit, and so on, such that lithiumis eluted from the columns with acid to produce a lithium concentrate.In one embodiment of the acid circuit, acid flows through a first columnin the acid circuit, then optionally into a next column in the acidcircuit, and so on, such that lithium is eluted from the columns withacid to produce a lithium concentrate. In one embodiment of the waterwashing circuit, water flows through a first column in the water washingcircuit, then optionally into a next column in the water washingcircuit, and so on, such that brine in the void space, pore space, orhead space of the columns in the water washing circuit is washed out.

In one embodiment of the column interchange system, ion exchange columnsare interchanged between the brine circuit, the water washing circuit,and the acid circuit. In one embodiment, the first column in the brinecircuit is loaded with lithium and then interchanged into the waterwashing circuit to remove brine from the void space, pore space, or headspace of the column. In one embodiment, the first column in the waterwashing circuit is washed to remove brine, and then interchanged to theacid circuit, where lithium is eluted with acid to form a lithiumconcentrate. In one embodiment, the first column in the acid circuit iseluted with acid and then interchanged into the brine circuit to absorblithium from the brine. In one embodiment of the column interchangesystem, two water washing circuits are used to wash the columns afterboth the brine circuit and the acid circuit. In one embodiment of thecolumn interchange system, only one water washing circuit is used towash the columns after the brine circuit, whereas excess acid isneutralized with base or washed out of the columns in the brine circuit.

In one embodiment of the column interchange system, the first column inthe brine circuit is interchanged to become the last column in the waterwashing circuit. In one embodiment of the column interchange system, thefirst column in the water washing circuit is interchanged to become thelast column in the acid circuit. In one embodiment of the columninterchange system, the first column in the acid circuit is interchangedto become the last column in the brine circuit.

In one embodiment of the column interchange system, each column in thebrine circuit contains one or more tanks or junctions for mixing baseinto the brine and optionally settling any basic precipitates that formfollowing base addition. In one embodiment of the column interchangesystem, each column in the brine circuit has associated one or moretanks or junctions for removing basic precipitates or other particlesvia settling or filtration. In one embodiment of the column interchangesystem, each column or various clusters of columns have associated oneor more settling tanks or filters that remove particles includingparticles that detach from ion exchange beads.

In one embodiment of the column interchange system, the number of thecolumns in the brine circuit is optionally less than about 3, less thanabout 10, less than about 30, or less than about 100. In one embodimentof the column interchange system, the number of the columns in the acidcircuit is optionally less than about 3, less than about 10, less thanabout 30, or less than about 100. In one embodiment of the columninterchange system, the number of the columns in the water washingcircuit is optionally less than about 3, less than about 10, less thanabout 30, or less than about 100. In certain embodiments, the number ofcolumns in the brine circuit is 1 to 10. In some embodiments, the numberof columns in the acid circuit is 1 to 10. In some embodiments, thenumber of columns in washing circuit is 1 to 10.

In one embodiment of the column interchange system, there is optionallyone or more brine circuits, one or more acid circuits, and one or morewater washing circuits. In one embodiment of the column interchangesystem, ion exchange columns are optionally supplied with fresh ionexchange beads without interruption to operating columns. In oneembodiment of the column interchange system, ion exchange columns withbeads that have been depleted in capacity is optionally replaced withion exchange columns with fresh ion exchange beads without interruptionto operating columns.

In one embodiment of the column interchange system, the columns containfluidized beds of ion exchange material. In one embodiment of the columninterchange system, the columns have means of created a fluidized bed ofion exchange material such as overhead stirrers or pumps. In oneembodiment of the column interchange system, the columns containfluidized beds of ion exchange material. In one embodiment of the ionexchange system, the system is an interchange system and the vessels arestirred tank reactors. In one embodiment of the interchange system, basemay be added directly to the columns or other tanks containing the ionexchange material. In one embodiment of the interchange system, base maybe added to the brine or another solution in a separate mixing tank andthen added to the columns or other tanks containing the ion exchangematerial.

In one embodiment of the ion exchange system, ion exchange beads areloaded into ion exchange columns and following lithium uptake frombrine, lithium is eluted from the ion exchange columns using an acidrecirculation loop. In one embodiment of the acid recirculation loop,acid is flowed through an ion exchange column, into a tank, and thenrecirculated through the ion exchange column to optimize lithiumelution. In one embodiment of the ion exchange system, ion exchangebeads are loaded into ion exchange columns and following lithium uptakefrom brine, lithium is eluted from each ion exchange column using aonce-through flow of acid. In one embodiment of the ion exchange system,ion exchange beads are loaded into an ion exchange column and followinglithium uptake from brine, lithium is eluted from the ion exchangecolumn using a column interchange circuit.

In one embodiment of the ion exchange system, ion exchange columns areloaded with lithium by flowing brine through the columns using arecirculating batch system and then lithium is eluted from the columnsusing a column interchange system. In one embodiment of the ion exchangesystem, ion exchange columns are loaded with lithium by flowing brinethrough the columns using a column interchange system and then lithiumis eluted from the columns using a recirculating batch system. In oneembodiment of the ion exchange system, ion exchange columns are loadedwith lithium by flowing brine through the columns using a recirculatingbatch system and then lithium is eluted from the columns using arecirculating batch system. In one embodiment of the ion exchangesystem, ion exchange columns are loaded with lithium by flowing brinethrough the columns using a column interchange system and then lithiumis eluted from the columns using a column interchange system.

Stirred Tank system

An aspect of the invention described herein is a system wherein the pHmodulating setup is a tank comprising: a) one or more compartments; andb) a means for moving the liquid resource through the one or morecompartments. In an embodiment, the ion exchange material is loaded inat least one compartment. In an embodiment, the means for moving theliquid resource through the one or more compartments is a pipe. In afurther embodiment, the means for moving the liquid resource through theone or more compartments is a pipe and suitably a configured pump. In anembodiment, the tank further comprises a means for circulating theliquid resource throughout the tank. In an embodiment, the means forcirculating the liquid resource throughout the tank is a mixing device.In an embodiment, the tank further comprises an injection port.

In some embodiments, the tank further comprises one or more injectionports. In some embodiments, the tank further comprises a plurality ofinjection ports.

An aspect described herein is a system for the extraction of lithiumions from a liquid resource, comprising a tank, wherein the tank furthercomprises: a) one or more compartments; b) an ion exchange material; c)a mixing device; and d) a pH modulating setup for changing the pH of thesystem, wherein the ion exchange material is used to extract lithiumions from the liquid resource. In one embodiment, the pH modulatingsetup changes the pH of the liquid resource in the system.

In some embodiments, the ion exchange material is loaded in at least oneof the one or more compartments. In some embodiments, the ion exchangematerial is fluidized in at least one of the one or more compartments.In some embodiments, the ion exchange material is non-fluidized in atleast one of the one or more compartments. In some embodiments, the ionexchange material occupies a fixed position in at least one of the oneor more compartments.

In some embodiments, the pH modulating setup comprises a pH measuringdevice and an inlet for adding base. In some embodiments, the pHmeasuring device is a pH probe. In some embodiments, the inlet is apipe. In some embodiments, the inlet is an injection port.

In some embodiments, the tank further comprises a porous partition. Insome embodiments, the porous partition is a porous polymer partition. Insome embodiments, the porous partition is a mesh or membrane. In someembodiments, the porous partition is a polymer mesh or polymer membrane.In some embodiments, the porous partition comprises one or more layersof mesh, membrane, or other porous structure. In some embodiments, theporous partition comprises one or more coarse meshes that providestructural support and one or more fine meshes and/or membranes thatprovide filtration. In some embodiments, the porous partition comprisesa polyether ether ketone mesh, a polypropylene mesh, a polyethylenemesh, a polysulfone mesh, a polyester mesh, a polyamide mesh, apolytetrafluoroethylene mesh, an ethylene tetrafluoroethylene polymermesh, a stainless steel mesh, a stainless steel mesh coated in polymer,a stainless steel mesh coated in ceramic, or a combination thereof,wherein the mesh is a course mesh, a fine mesh, or a combinationthereof. In some embodiments, the porous polymer partition comprises amesh comprising one or more blends of two or more of a polyether etherketone, a polypropylene, a polyethylene, a polysulfone, a polyester, apolyamide, a polytetrafluoroethylene, or an ethylene tetrafluoroethylenepolymer. In some embodiments, the porous partition comprises a polyetherether ketone membrane, a polypropylene membrane, a polyethylenemembrane, a polysulfone membrane, a polyester membrane, a polyamidemembrane, a polytetrafluoroethylene membrane, an ethylenetetrafluoroethylene polymer membrane, or combinations thereof.

In one embodiment of the ion exchange system, the system is a stirredtank system comprised of a tank of brine containing permeable beadcompartments such as permeable pallets, cases, boxes, or othercontainers that are loaded with ion exchange beads, and the brine isstirred through the tank in a batch process. In one embodiment of thestirred tank system, the base is optionally added directly to the tankgradually or all at once as a solid or in an aqueous solution. In oneembodiment of the stirred tank system, after a brine uptake stage iscomplete, the permeable bead containers are optionally moved to anothertank for acid elution. In one embodiment of the stirred tank system, thepermeable bead compartments are located at the bottom of the stirredtank during the brine stage and after the brine stage is completed, thenbrine is removed, and the bottom of the stirred tank is filled with acidto elute lithium in such a way that the permeable bead compartments arecovered with an optimal volume of acid.

In one embodiment of the stirred tank system, the ion exchange beads aresuspended using plastic structural supports in a tank with an internalmixing device. In one embodiment of the stirred tank system, a stream ofbrine is removed from the tank and passed through a column wherehydrogen ions in the brine produced by ion exchange are neutralizedusing sacrificial base in solution or added as solid, or by an ionexchange resin. This pH-corrected stream is sent back into the systemwhere the lithium can continue to be removed. In one embodiment of thestirred tank system, brine that has passed through the bead compartmentis returned to the opposite end of the tank through a pipe that isoptionally internal or external to the tank. In one embodiment of thestirred tank system, base is optionally added to the brine inside thetank or in a base addition tank outside the tank.

In one embodiment of the stirred tank system, fresh brine is fed to thesystem so as to operate in continuous stirred tank system mode insteadof batch mode. In one embodiment of the recirculating batch system,fresh brine is fed to the system so as to operate in continuous stirredtank system mode instead of batch mode.

In one embodiment of the ion exchange system, the ion exchange materialis mixed with a liquid resource in a stirred tank reactor. In oneembodiment, the ion exchange material may be comprised of coatedparticles, uncoated particles, porous beads, or combinations thereof.

In one embodiment of the ion exchange system, a stirred tank reactor isused to fluidize the ion exchange material in a liquid resource toenable absorption of lithium from the liquid resource into the ionexchange material. In one embodiment, a stirred tank reactor is used tofluidize the ion exchange material in a washing fluid to remove residualbrine, acid, or other contaminants from the ion exchange materials. Inone embodiment, a stirred tank reactor is used to fluidize the ionexchange material in an acid solution to elute lithium from the ionexchange material while replacing the lithium in the ion exchangematerial with protons. In one embodiment, a single stirred tank reactoris used to mix ion exchange material with a liquid resource, washingfluid, and acid solution.

In some embodiments, the system for the extraction of lithium ions froma liquid resource, comprising a tank, wherein the tank furthercomprises: a) one or more compartments; b) an ion exchange material; c)a mixing device; and d) a pH modulating setup for changing the pH of theliquid resource in the system, wherein the ion exchange material is usedto extract lithium ions from the liquid resource, further comprisesanother tank, wherein the other tank further comprises: a) one or morecompartments; b) an ion exchange material; c) a mixing device; and d) apH modulating setup for changing the pH of the liquid resource in thesystem. In some embodiments, the tank is in fluid communication with theother tank.

In some embodiments, the system for the extraction of lithium ions froma liquid resource, comprising a tank, wherein the system furthercomprises another tank, wherein the other tank further comprises: a) oneor more compartments; b) an ion exchange material; c) a mixing device;and d) an acid inlet for adding acid to the system. In a furtherembodiment, the ion exchange material is moved between the tank and theother tank.

In some embodiments, the system for the extraction of lithium ions froma liquid resource, comprising a tank, wherein the tank furthercomprises: a) one or more compartments; b) an ion exchange material; c)a mixing device; and d) a pH modulating setup for changing the pH of theliquid resource in the system, wherein the ion exchange material is usedto extract lithium ions from the liquid resource, further comprises aplurality of tanks, each tank further comprising: a) one or morecompartments; b) an ion exchange material; c) a mixing device; and d) apH modulating setup for changing the pH of the liquid resource in thesystem. In some embodiments, each tank of the system is in fluidcommunication with each other tank of the system.

In some embodiments, the system further comprises another plurality oftanks, wherein each tank further comprises: a) one or more compartments;b) an ion exchange material; and c) a mixing device.

In some embodiments, the system is configured to operate in a batchmode. In some embodiments, the system is configured to operate in acontinuous mode. In some embodiments, the system is configured tooperate in a batch mode and a continuous mode. In some embodiments, oneor more tanks in the system are configured to operate in a batch modeand one or more tanks in the system are configured to operate in acontinuous mode. In some embodiments, one or more tanks in the systemare configured to operate in a batch mode and one or more tanks in thesystem are configured to operate in a semi-continuous mode. In someembodiments, one or more tanks in the system are configured to operatein a semi-continuous mode and one or more tanks in the system areconfigured to operate in a continuous mode. In some embodiments, one ormore tanks in the system are configured to operate in a batch mode, oneor more tanks in the system are configured to operate in asemi-continuous mode, and one or more tanks in the system are configuredto operate in a continuous mode. In some embodiments, the system isconfigured to operate in a semi-continuous mode, a batch mode, acontinuous mode, or combinations thereof.

In one embodiment of the ion exchange system, a plurality of stirredtank reactors are used to mix ion exchange material with a liquidresource, washing fluid, and acid solution. In one embodiment, thestirred tank reactors may be different sizes and may contain differentvolumes of a liquid resource, washing fluid, and acid solution. In oneembodiment, the stirred tanks may be cylindrical, conical, rectangular,pyramidal, or a combination thereof. In one embodiment of the ionexchange system, the ion exchange material may move through theplurality of stirred tank reactors in the opposite direction of theliquid resource, the washing fluid, or the acid solution.

In one embodiment of the ion exchange system, a plurality of stirredtank reactors may be used where one or more stirred tank reactors mixthe ion exchange material with a liquid resource, one or more stirredtank reactors mix the ion exchange material with a washing fluid, andone or more stirred tank reactors mix the ion exchange material with anacid solution.

In one embodiment of the ion exchange system, stirred tank reactors maybe operated in a continuous, semi-continuous, or batch mode where aliquid resource flows continuously, semi-continuously, or batch-wisethrough the stirred tank reactor. In one embodiment of the ion exchangesystem, stirred tank reactors may be operated in a continuous,semi-continuous, or batch mode where the ion exchange material flowscontinuously, semi-continuously, or batch-wise through the stirred tankreactor. In one embodiment of the ion exchange system, stirred tankreactors may be operated in a mode where the ion exchange materialremains in the tank while flows of liquid resource, washing fluid, oracid solution are flowed through the tank in continuous,semi-continuous, or batch flows.

In one embodiment, ion exchange material may be loaded into or removedfrom the stirred tank reactors through the top, the bottom, or the sideof the tank.

In one embodiment of the ion exchange system, stirred tank reactors maycomprise one or more compartments. In one embodiment, the compartmentsmay contain ion exchange material in a bed that is fluidized, fixed,partially fluidized, partially fixed, alternatively fluidized,alternatively fixed, or combinations thereof. In one embodiment, thecompartments may be comprised of a porous support at the bottom of thecompartment, the sizes of the compartment, the top of the compartment,or combinations thereof. In one embodiment, the compartments may beconical, cylindrical, rectangular, pyramidal, other shapes, orcombinations thereof. In one embodiment, the compartment may be locatedat the bottom of the tank. In one embodiment, the shape of thecompartment may conform to the shape of the stirred tank reactor. In oneembodiment, the compartment may be partially or fully comprised of thetank of the stirred tank reactor.

In one embodiment, the compartment may be comprised of a porousstructure. In one embodiment, the compartment may be comprised of apolymer, a ceramic, a metal, or combinations thereof. In one embodiment,the compartment may be comprised be comprised partially or fully of aporous material or a mesh. In one embodiment, the compartment may be atthe top of the tank. In one embodiment, the compartment may be separatedfrom the rest of the tank with one or more porous materials. In oneembodiment, the compartment may be at the top of the tank. In oneembodiment, the compartment may be separated from the rest of the tankwith a bilayer mesh comprising one layer of coarse mesh for strength andone layer of fine mesh to contain smaller particles in the compartment.In one embodiment, the compartment may allow liquid to flow freelythrough the stirred tank reactor and through the compartment. In oneembodiment, the compartment may be open on the top. In one embodiment,the compartment may contain the ion exchange material in the tank butallow the ion exchange material to move throughout the tank. In oneembodiment, the compartment may comprise a majority or minority of thetank volume. In one embodiment, the compartment may represent a fractionof the volume of the tank that is greater than 1 percent, greater than10 percent, greater than 50 percent, greater than 90 percent, greaterthan 99 percent, or greater than 99.9 percent. In one embodiment, one ormore devices for stirring, mixing, or pumping may be used to move fluidthrough the compartment, the stirred tank reactor, or combinationsthereof.

In one embodiment of the ion exchange system, stirred tank reactors maybe arranged into a network where flows of brine, washing fluid, and acidsolutions are directly through different columns. In one embodiment, anetwork of stirred tank reactors may involve physical movement of theion exchange material through the various stirred tank reactors. In oneembodiment, a network of stirred tank reactors may involve no physicalmovement of the ion exchange material through the various stirred tankreactors. In one embodiment, a network of stirred tank reactors mayinvolve switching of flows of brine, washing fluid, and acid solutionsthrough the various stirred tank reactors. In one embodiment, brine mayinto stirred tank reactors in continuous or batch mode. In oneembodiment, brine may be mixed with ion exchange material in one or morereactors before exiting the system. In one embodiment, a network ofstirred tank reactors may involve a brine circuit with counter-currentexposure of ion exchange material to flows of brine. In one embodiment,a network of stirred tank reactors may involve a washing circuit withcounter-current exposure of ion exchange material to flows of washingfluid. In one embodiment, a network of stirred tank reactors may involvean acid circuit with counter-current exposure of ion exchange materialto flows of acid solution. In one embodiment, the washing fluid may bewater, an aqueous solution, or a solution containing an anti-scalant.

In one embodiment of the stirred tank reactor, acid is added at thebeginning of elution. In one embodiment of the stirred tank reactor,acid is added at the beginning of elution and again during elution. Inone embodiment of the stirred tank reactor, an acid of lowerconcentration is added at the start of elution and additional acid ofhigh concentration is added to continue elution.

An aspect described herein is a system for the extraction of lithiumions from a liquid resource, comprising: a) an ion exchange material; b)a tank comprising one or more compartments; and c) a mixing device,wherein the ion exchange material is used to extract lithium ions fromthe liquid resource.

In some embodiments, the ion exchange material is loaded in at least oneof the one or more compartments. In some embodiments, the ion exchangematerial is fluidized or partially fluidized in at least one of the oneor more compartments. In some embodiments, the ion exchange materialoccupies a fixed position in at least one of the one or morecompartments. In some embodiments, the ion exchange material is mountedin at least one of the one or more compartments.

An aspect described herein is a system for the extraction of lithiumions from a liquid resource, comprising: a) a column comprising an ionexchange material; and b) a pH modulating setup for changing the pH ofthe liquid resource in the system, wherein the pH modulating setup is influid communication with the column, wherein the ion exchange materialis used to extract lithium ions from the liquid resource.

Other Types of Systems

An aspect described herein is a system for the extraction of lithiumions from a liquid resource, comprising: a) a plurality of columns,wherein each of the plurality of columns comprises an ion exchangematerial; and b) a pH modulating setup for changing the pH of the liquidresource in the system, wherein the pH modulating setup is in fluidcommunication with each of the plurality of columns, wherein the ionexchange material is used to extract lithium ions from the liquidresource.

In some embodiments, the pH modulating setup comprises a plurality oftanks, wherein each of the plurality of tanks is immediately connectedto one of the plurality of columns. In one embodiment, the pH modulatingsetup comprises a plurality of tanks, wherein each of the plurality oftanks is in immediate liquid communication with one of the plurality ofcolumns. In some embodiments, two or more of the plurality of tanksconnected to two or more of the plurality of columns forms at least onecircuit. In some embodiments, two or more of the plurality of tanksconnected to two or more of the plurality of columns forms at least twocircuits. In some embodiments, three or more of the plurality of tanksconnected to three or more of the plurality of columns forms at leasttwo circuits. In some embodiments, three or more of the plurality oftanks connected to three or more of the plurality of columns forms atleast three circuits.

In some embodiments, at least one circuit is a liquid resource circuit.In some embodiments, at least one circuit is a water washing circuit. Insome embodiments, at least two circuits are water washing circuits. Insome embodiments, at least one circuit is an acid solution circuit.

An aspect described herein is a system for the extraction of lithiumions from a liquid resource comprising an ion exchange material and aplurality of vessels, wherein each of the plurality of vessels isconfigured to transport the ion exchange material along the length ofthe vessel and the ion exchange material is used to extract lithium ionsfrom the liquid resource. In some embodiments, at least one of theplurality of vessels comprises an acidic solution. In some embodiments,at least one of the plurality of vessels comprises the liquid resource.In some embodiments, each of the plurality of vessels is configured totransport the ion exchange material by a pipe system or an internalconveyer system.

An aspect described herein is a system for the extraction of lithiumions from a liquid resource comprising an ion exchange material and aplurality of columns, wherein each of the plurality of columns isconfigured to transport the ion exchange material along the length ofthe column and the ion exchange material is used to extract lithium ionsfrom the liquid resource.

In some embodiments, at least one of the plurality of columns comprisesan acidic solution. In some embodiments, at least one of the pluralityof columns comprises the liquid resource. In some embodiments, each ofthe plurality of columns is configured to transport the ion exchangematerial by a pipe system or an internal conveyer system.

In some embodiments, the ion exchange material comprises ion exchangeparticles. In some embodiments, at least a portion of the ion exchangematerial is in the form of ion exchange particles. In some embodiments,the ion exchange particles are selected from uncoated ion exchangeparticles, coated ion exchange particles, and combinations thereof. Insome embodiments, the ion exchange particles comprise uncoated ionexchange particles. In some embodiments, the ion exchange particlescomprise coated ion exchange particles. In some embodiments, the ionexchange particles comprise a mixture of uncoated and coated ionexchange particles.

In some embodiments, the coated ion exchange particles comprise an ionexchange material and a coating material.

In some embodiments, the coating material of the coated ion exchangeparticles comprises a carbide, a nitride, an oxide, a phosphate, afluoride, a polymer, carbon, a carbonaceous material, or combinationsthereof. In some embodiments, the coating material of the coated ionexchange particles is selected from the group consisting of TiO₂, ZrO₂,MoO₂, SnO₂, Nb₂O₅, Ta₂O₅, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂SiO₃, Li₂MnO₃,Li₂MoO₃, LiNbO₃, LiTaO₃, AlPO₄, LaPO₄, ZrP₂O₇, MoP₂O₇, Mo₂P₃O₁₂, BaSO₄,AlF₃, SiC, TiC, ZrC, Si₃N₄, ZrN, BN, carbon, graphitic carbon, amorphouscarbon, hard carbon, diamond-like carbon, solid solutions thereof, andcombinations thereof.

In some embodiments, the ion exchange material of the coated ionexchange particles comprises an oxide, a phosphate, an oxyfluoride, afluorophosphate, or combinations thereof. In some embodiments, the ionexchange material of the coated ion exchange particles is selected fromthe group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂, Li₂TiO₃, Li₂MnO₃, Li₂SnO₃,LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂, LiTiO₂, Li₄TiO₄,Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄, Li₂CuP₂O₇, Al(OH)₃,LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O, TiO₂.xSb₂O₅.yH₂O, solid solutionsthereof, and combinations thereof; wherein xis from 0.1-10; and y isfrom 0.1-10.

In some embodiments, the uncoated ion exchange particles comprise an ionexchange material. In some embodiments, the ion exchange material of theuncoated ion exchange particles comprises an oxide, a phosphate, anoxyfluoride, a fluorophosphate, or combinations thereof. In someembodiments, the ion exchange material of the uncoated ion exchangeparticles is selected from the group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂,Li₂TiO₃, Li₂MnO₃, Li₂SnO₃, LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂,LiTiO₂, Li₄TiO₄, Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄,Li₂CuP₂O₇, Al(OH)₃, LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O,TiO₂.xSb₂O₅.yH₂O, solid solutions thereof, and combinations thereof;wherein xis from 0.1-10; and y is from 0.1-10.

In some embodiments, the ion exchange material is porous. In someembodiments, the porous ion exchange material comprises a network ofpores that allows liquids to move quickly from the surface of the porousion exchange material to a plurality of ion exchange particles. In someembodiments, the porous ion exchange material comprises a network ofpores that allows a liquid to move from the surface of the porous ionexchange material to a plurality of ion exchange particles. In someembodiments, the porous ion exchange material comprises a network ofpores that allows a liquid to move quickly from the surface of theporous ion exchange material to a plurality of ion exchange particles.In some embodiments, the porous ion exchange material is porous ionexchange beads. In some embodiments, the porous ion exchange material iscomprised of porous ion exchange beads.

In some embodiments of the systems described herein, the liquid resourceis a natural brine, a dissolved salt flat, seawater, concentratedseawater, a desalination effluent, a concentrated brine, a processedbrine, waste brine from a bromine-extraction process, an oilfield brine,a liquid from an ion exchange process, a liquid from a solventextraction process, a synthetic brine, a leachate from an ore orcombination of ores, a leachate from a mineral or combination ofminerals, a leachate from a clay or combination of clays, a leachatefrom recycled products, a leachate from recycled materials, orcombinations thereof. In some embodiments of the systems describedherein, the liquid resource is a brine. In some embodiments of thesystems described herein, the liquid resource comprises a natural brine,a synthetic brine, or a mixture of a natural and a synthetic brine. Insome embodiments of the systems described herein, the liquid resource isa natural brine, a dissolved salt flat, seawater, concentrated seawater,a desalination effluent, a concentrated brine, a processed brine, wastebrine from a bromine-extraction process, an oilfield brine, a liquidfrom an ion exchange process, or combinations thereof.

An aspect of the invention described herein is a system, wherein thecolumn further comprises a plurality of injection ports, wherein theplurality of injection ports are used to increase the pH of the liquidresource in the system

In one embodiment of the ion exchange system, the system is a mixed basesystem comprising an ion exchange column and a mixing chamber where baseis mixed into the brine immediately prior to injection of the brine intothe column.

In one embodiment of the ion exchange system, the system is a ported ionexchange column system with multiple ports for injection of aqueous basespaced at intervals along the direction of brine flow through thecolumn. As brine flows through the column, there is a region of thecolumn where the beads experience the greatest rate of lithiumabsorption, and this region moves through the column in the direction ofbrine flow. In the ported ion exchange column system, base is injectednear that region to neutralize protons released by the ion exchangereaction. In regions of the columns where the beads have been saturatedwith lithium and the rate of release of protons has slowed, baseinjected is decreased or terminated to avoid formation of basicprecipitates.

In one embodiment of the ion exchange system, the system has a movingbed of beads that moves in a direction opposite to the flow of brine andbase is injected at one or more fixed points in the column in a regionnear where the ion exchange reaction occurs at a maximum rate in thecolumn to neutralize the protons released from the ion exchangereaction. In one embodiment of the ion exchange system, the base addedto the brine is optionally NaOH, KOH, Mg(OH)₂, Ca(OH)₂, CaO, NH₃,Na₂SO₄, K₂SO₄, NaHSO₄, KHSO₄, NaOCl, KOCl, NaClO₄, KClO₄, NaH₂BO₄,Na₂HBO₄, Na₃BO₄, KH₂BO₄, K₂HBO₄, K₃BO₄, MgHBO₄, CaHBO₄, NaHCO₃, KHCO₃,NaCO₃, KCO₃, MgCO₃, CaCO₃, Na₂O, K₂O, Na₂CO₃, K₂CO₃, Na₃PO₄, Na₂HPO₄,NaH₂PO₄, K₃PO₄, K₂HPO₄, KH₂PO₄, CaHPO₄, MgHPO₄, sodium acetate,potassium acetate, magnesium acetate, poly(vinylpyridine),poly(vinylamine), polyacrylonitrile, other bases, or combinationsthereof. In one embodiment, the base is optionally added to the brine inits pure form or as an aqueous solution. In one embodiment, the base isoptionally added in a gaseous state such as gaseous NH₃. In oneembodiment, the base is optionally added to the brine in a steadystream, a variable stream, in steady aliquots, or in variable aliquots.In one embodiment, the base is optionally created in the brine by usingan electrochemical cell to remove H₂ and Cl₂ gas, which is optionallycombined in a separate system to create HCl acid to be used for elutinglithium from the system or for other purposes.

In some embodiments, a solid base is mixed with a liquid resource tocreate a basic solution. In some embodiments, a solid base is mixed witha liquid resource to create a basic solution, and the resulting basicsolution is added to a second volume of a liquid resource to increasethe pH of the second volume of the liquid resource. In some embodiments,solid base is mixed with a liquid resource to create a basic solution,wherein the resulting basic solution is used to adjust or control the pHof a second solution. In some embodiments, a solid base is mixed with aliquid resource to create a basic slurry. In some embodiments, a solidbase is mixed with a liquid resource to create a basic slurry, and theresulting basic slurry is added to a second volume of a liquid resourceto increase the pH of the second volume of the liquid resource. In someembodiments, solid base is mixed with a liquid resource to create abasic slurry, wherein the resulting basic slurry is used to adjust orcontrol the pH of a second solution. In some embodiments, base may beadded to a liquid resource as a mixture or slurry of base and liquidresource.

In one embodiment of the ion exchange system, the brine flows through apH control column containing solid sacrificial base particles such asNaOH, CaO, or Ca(OH)₂, which dissolve into the brine and raise the pH ofthe brine. In one embodiment of the ion exchange system, the brine flowsthrough a pH control column containing immobilized regeneratableOH-containing ion exchange resins which react with hydrogen ions, orregeneratable base species such as immobilized polypyridine, whichconjugate HCl, thereby neutralizing the acidified brine. When the ionexchange resin has been depleted of its OH groups or is saturated withHCl, it is optionally regenerated with a base such as NaOH.

In one embodiment of the ion exchange system, pH meters are optionallyinstalled in tanks, pipes, column, and other components of the system tomonitor pH and control the rates and amounts of base addition at variouslocations throughout the system.

In one embodiment of the ion exchange system, the columns, tanks, pipes,and other components of the system are optionally constructed usingplastic, metal with a plastic lining, or other materials that areresistant to corrosion by brine or acid.

In one embodiment of the ion exchange system, the ion exchange columnsare optionally washed with water that is mildly acidic, optionallyincluding a buffer, to remove any basic precipitates from the columnprior to acid elution.

After the ion exchange column is saturated or nearly saturated withlithium, the lithium is flushed out of the ion exchange column usingacid. The acid is optionally flowed through the column one or more timesto elute the lithium. In one embodiment, the acid is optionally flowedthrough the ion exchange column using a recirculating batch systemcomprised of the ion exchange column connected to a tank. In oneembodiment, the tank used for acid flows is optionally the same tankused for the brine flows. In a further embodiment, the tank used foracid flows is optionally a different tank than the one used for brineflows. In a further embodiment, the acid is distributed at the top ofthe ion exchange column and allowed to percolate through and immediatelyrecirculated into the column with no extra tank. In an embodiment, acidaddition optionally occurs without a tank used for acid flows.

In one embodiment of the ion exchange system, the column is optionallywashed with water after the brine and/or acid steps, and the effluentwater from washing is optionally treated using pH neutralization andreverse osmosis to yield process water.

In one embodiment of the ion exchange system, the ion exchange column isoptionally shaped like a cylinder, a rectangle, or another shape. In oneembodiment, the ion exchange column optionally has a cylinder shape witha height that is greater or less than its diameter. In one embodiment,the ion exchange column optionally has a cylinder shape with a heightthat is less than 10 cm, less than 1 meter, or less than 10 meters. Inone embodiment, the ion exchange column optionally has a cylinder shapewith a diameter that is less than 10 cm, less than 1 meter, or less than10 meters.

In one embodiment of the ion exchange system, the system is optionallyresupplied with fresh ion exchange beads by swapping out an ion exchangecolumn with a new column loaded with fresh ion exchange beads. In oneembodiment of the ion exchange system, the system is optionallyresupplied with fresh ion exchange beads by removing the beads from thecolumn and loading new beads into the column. In one embodiment of theion exchange system, new beads are optionally supplied to all columns inthe system simultaneously. In one embodiment of the ion exchange system,new beads are optionally supplied to one or more columns at a time. Inone embodiment of the ion exchange system, new beads are optionallysupplied to one or more columns without interruption to other columnsthat optionally continue operating.

In one embodiment of the ion exchange system, brine pumping optionallycontinues until the ion exchange beads approach a point of lithiumsaturation over a period of time that is optionally less than about 1hours, less than about 2 hours, less than about 4 hours, less than about8 hours, less than about 24 hours, less than about 48 hours, or lessthan about one week. In one embodiment of the ion exchange system, brinepumping optionally continues until the ion exchange beads approach apoint of lithium saturation over a period of time that is optionallygreater than about one week. In certain embodiments of the ion exchangesystem, brine pumping optionally continues until the ion exchange beadsapproach a point of lithium saturation over a period of time that isoptionally between 30 minutes and 24 hours. In one embodiment of the ionexchange system, acid pumping optionally continues until the ionexchange beads approach a point of hydrogen saturation over a period oftime that is optionally less than about 1 hours, less than about 2hours, less than about 4 hours, less than about 8 hours, less than about24 hours, or less than about 48 hours. In one embodiment of the ionexchange system, brine pumping optionally continues until the ionexchange beads approach a point of hydrogen saturation over a period oftime that is optionally greater than about one 48 hours. In certainembodiments of the ion exchange system, brine pumping optionallycontinues until the ion exchange beads approach a point of hydrogensaturation over a period of time that is optionally between 30 minutesand 24 hours.

Ion Exchange Material

An aspect of the invention described herein is a system wherein the ionexchange material comprises a plurality of ion exchange particles. In anembodiment, the plurality of ion exchange particles in the ion exchangematerial is selected from uncoated ion exchange particles, coated ionexchange particles and combinations thereof. In an embodiment, the ionexchange material is a porous ion exchange material. In an embodiment,the porous ion exchange material comprises a network of pores thatallows liquids to move quickly from the surface of the porous ionexchange material to the plurality of ion exchange particles. In anembodiment, the ion exchange material is in the form of porous ionexchange beads. In an embodiment, the liquid resource is a naturalbrine, a dissolved salt flat, seawater, concentrated seawater, adesalination effluent, a concentrated brine, a processed brine, anoilfield brine, a liquid from an ion exchange process, a liquid from asolvent extraction process, a synthetic brine, a leachate from an ore orcombination of ores, a leachate from a mineral or combination ofminerals, a leachate from a clay or combination of clays, a leachatefrom recycled products, a leachate from recycled materials, orcombinations thereof.

Ion exchange materials are typically small particles, which togetherconstitute a fine powder. In some embodiments small particle sizeminimizes the diffusion distance that lithium must travel into the coreof the ion exchange particles. In some cases, these particles areoptionally coated with protective surface coatings to minimizedissolution of the ion exchange materials while allowing efficienttransfer of lithium and hydrogen to and from the particles.

In an embodiment, the coated ion exchange particles are comprised of anion exchange material and a coating material wherein the ion exchangematerial comprises Li₄Mn₅O₁₂, Li_(1.6)Mn_(1.6)O₄, Li₂MO₃ (M=Ti, Mn, Sn),LiFePO₄, solid solutions thereof, or combinations thereof and thecoating material comprises TiO₂, ZrO₂, MoO₂, Li₂TiO₃, Li₂ZrO₃, LiNbO₃,AlF₃, SiC, Si₃N₄, graphitic carbon, amorphous carbon, diamond-likecarbon, or combinations thereof. The coated ion exchange particles havean average diameter less than about 100 nm, less than about 1,000 nm, orless than about 10,000 nm, and the coating thickness is less than about1 nm, less than about 10 nm, or less than about 100 nm. The particlesare created by first synthesizing the ion exchange material using amethod such as hydrothermal, solid state, or microwave. The coatingmaterial is then deposited on the surface of the ion exchange materialusing a method such as chemical vapor deposition, hydrothermal,solvothermal, sol-gel, precipitation, or microwave. The coated ionexchange particles are treated with an acid solution prepared withhydrochloric acid, sulfuric acid, nitric acid, or combinations thereofwherein the concentration of the acid solution is greater than about 0.1M, greater than about 1.0 M, greater than about 5 M, greater than about10 M, or combinations thereof. During acid treatment, the particlesabsorb hydrogen while releasing lithium. The ion exchange material isconverted to a hydrated state with a hydrogen-rich composition. Thecoating material allows diffusion of hydrogen and lithium respectivelyto and from the ion exchange material while providing a protectivebarrier that limits dissolution of the ion exchange material. Aftertreatment in acid, the hydrated coated ion exchange particles aretreated with a liquid resource wherein the liquid resource is a naturalbrine, a dissolved salt flat, a concentrated brine, a processed brine, asynthetic brine, liquid from an ion exchange process, liquid from asolvent extraction process, leachate from minerals, leachate from clays,leachate from recycled products, leachate from recycled materials, orcombinations thereof. The coated ion exchange particles absorb lithiumwhile releasing hydrogen. The lithium salt solution is then collected.The coated ion exchange particles are capable then perform the ionexchange reaction repeatedly over a number of cycles greater than about10 cycles, greater than about 30 cycles, greater than about 100 cycles,or greater than about 300 cycles.

One major challenge for lithium extraction using inorganic ion exchangeparticles is the loading of the particles into an ion exchange column insuch a way that brine and acid are optionally pumped efficiently throughthe column with minimal clogging. The materials are optionally formedinto beads, and the beads are optionally loaded into the column. Thisbead loading creates void spaces between the beads, and these voidspaces facilitate pumping through the column. The beads hold the ionexchange particles in place and prevent free movement of the particlesthroughout the column. When the materials are formed into beads, thepenetration of brine and acid solutions into the beads become slow andchallenging. A slow rate of convection and diffusion of the acid andbrine solutions into the bead slows the kinetics of lithium absorptionand release. Such slow kinetics can create problems for columnoperation. Slow kinetics can require slow pumping rates through thecolumn. Slow kinetics can also lead to low lithium recovery from thebrine and inefficient use of acid to elute the lithium.

In some embodiments, the ion exchange beads are porous ion exchangebeads with networks of pores that facilitate the transport into thebeads of solutions that are pumped through an ion exchange column. Porenetworks are optionally strategically controlled to provide fast anddistributed access for the brine and acid solutions to penetrate intothe bead and deliver lithium and hydrogen to the ion exchange particles.One example of a porous ion exchange bead is shown in FIG. 8.

In some embodiments, the ion exchange beads are formed by mixing ionexchange particles, a matrix material, and a filler material. Thesecomponents are mixed and formed into a bead. Then, the filler materialis removed from the bead to leave behind pores. The filler material isdispersed in the bead in such a way to leave behind a pore structurethat enables transport of lithium and hydrogen with fast kinetics. Thismethod optionally involves multiple ion exchange materials, multiplepolymer materials, and multiple filler materials.

Another major challenge for lithium extraction using inorganic ionexchange materials is dissolution and degradation of the materials,especially during lithium elution in acid but also during lithium uptakein liquid resources. To yield a concentrated lithium solution from theion exchange process, it is desirable to use a concentrated acidsolution to elute the lithium. However, concentrated acid solutionsdissolve and degrade inorganic ion exchange materials, which decreasethe performance and lifespan of the materials. Therefore, the porous ionexchange beads optionally contain coated ion exchange particle forlithium extraction that are comprised of an ion exchange material and acoating material protecting the particle surface. The coating protectsthe ion exchange material from dissolution and degradation duringlithium elution in acid, during lithium uptake from a liquid resource,and during other aspects of an ion exchange process. This coatedparticle enables the use of concentrated acids in the ion exchangeprocess to yield concentrated lithium solutions. One example of a coatedion exchange particle is shown in FIG. 7.

In this invention, the ion exchange material is selected for highlithium absorption capacity, high selectivity for lithium in a liquidresource relative to other ions such as sodium and magnesium, stronglithium uptake in liquid resources including those with lowconcentrations of lithium, facile elution of lithium with a small excessof acid, and fast ionic diffusion. A coating material is optionallyselected to protect the particle from dissolution and chemicaldegradation during lithium recovery in acid and also during lithiumuptake in various liquid resources. A coating material optionally isalso selected to facilitate diffusion of lithium and hydrogen betweenthe particles and the liquid resources, to enable adherence of theparticles to a structural support, and to suppress structural andmechanical degradation of the particles.

When the porous ion exchange beads are used in an ion exchange column,the liquid resource containing lithium is pumped through the ionexchange column so that the ion exchange particles absorb lithium fromthe liquid resource while releasing hydrogen. After the beads haveabsorbed lithium, an acid solution is pumped through the column so thatthe particles release lithium into the acid solution while absorbinghydrogen. The column is optionally operated in co-flow mode with theliquid resource and acid solution alternately flowing through the columnin the same direction, or the column is optionally operated incounter-flow mode with a liquid resource and acid solution alternatelyflowing through the column in opposite directions. Between flows of theliquid resource and the acid solution, the column is optionally treatedor washed with water or other solutions for purposes such as adjustingpH in the column or removing potential contaminants. The beadsoptionally form a fixed or moving bed, and the moving bed optionallymoves in counter-current to the brine and acid flows. The beads areoptionally moved between multiple columns with moving beds wheredifferent columns are used for brine, acid, water, or other flows.Before or after the liquid resource flows through the column, the pH ofthe liquid is optionally adjusted with NaOH or other chemicals tofacilitate the ion exchange reaction as well as handling or disposal ofthe spent liquid resource. Before or after the liquid resource flowsthrough the column, the liquid resource is optionally subjected to otherprocesses including other ion exchange processes, solvent extraction,evaporation, chemical treatment, or precipitation to remove lithium, toremove other chemical species, or to otherwise treat the brine.

When the ion exchange particles are treated with acid, a lithiumsolution is produced. This lithium solution is optionally furtherprocessed to produce lithium chemicals. These lithium chemicals areoptionally supplied for an industrial application. In some embodiments,an ion exchange material is selected from the following list: an oxide,a phosphate, an oxyfluoride, a fluorophosphate, or combinations thereof.In some embodiments, an ion exchange material is selected from thefollowing list: LiFePO₄, LiMnPO₄, Li₂MO₃ (M=Ti, Mn, Sn), Li₄Ti₅O₁₂,Li₄Mn₅O₁₂, LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiMO₂ (M=Al, Cu, Ti), Li₄TiO₄,Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, Li₂CuP₂O₇, Al(OH)₃, LiCl.xAl(OH)₃.yH₂O,SnO₂.xSb₂O₅.yH₂O, TiO₂.xSb₂O₅.yH₂O, solid solutions thereof, orcombinations thereof. In a further aspect, an ion exchange materialcomprises LiFePO₄, Li₂SnO₃, Li₂MnO₃, Li₂TiO₃, Li₄Ti₅O₁₂, Li₄Mn₅O₁₂,Li_(1.6)Mn_(1.6)O₄, solid solutions thereof, or combinations thereof.

In a further aspect described herein, the coating material allowsdiffusion to and from the ion exchange material. In particular, thecoating material facilitates diffusion of lithium and hydrogen betweenthe particles and the liquid resources, enables adherence of theparticles to a structural support, and suppresses structural andmechanical degradation of the particles. In a further aspect describedherein, the coating material comprises a carbide, a nitride, an oxide, aphosphate, a fluoride, a polymer, carbon, a carbonaceous material, orcombinations thereof. In a further aspect, the coating materialcomprises polyvinylidene difluoride, polyvinyl chloride, afluoro-polymer, a chloro-polymer, or a fluoro-chloro-polymer. In afurther aspect, a coating material comprises Nb₂O₅, Ta₂O₅, MoO₂, TiO₂,ZrO₂, SnO₂, SiO₂, Li₂O, Li₂TiO₃, Li₂ZrO₃, Li₂MoO₃, LiNbO₃, LiTaO₃,Li₂SiO₃, Li₂Si₂O₅, Li₂MnO₃, ZrSiO₄, AlPO₄, LaPO₄, ZrP₂O₇, MoP₂O₇,Mo₂P₃O₁₂, BaSO₄, AlF₃, SiC, TiC, ZrC, Si₃N₄, ZrN, BN, carbon, graphiticcarbon, amorphous carbon, hard carbon, diamond-like carbon, solidsolutions thereof, or combinations thereof. In a further aspect, acoating material comprises TiO₂, ZrO₂, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂MnO₃,ZrSiO₄, or LiNbO₃. In a further aspect, a coating material comprises achloro-polymer, a fluoro-polymer, a chloro-fluoro-polymer, a hydrophilicpolymer, a hydrophobic polymer, co-polymers thereof, mixtures thereof,or combinations thereof. In a further aspect, a coating materialcomprises a co-polymer, a block co-polymer, a linear polymer, a branchedpolymer, a cross-linked polymer, a heat-treated polymer, a solutionprocessed polymer, co-polymers thereof, mixtures thereof, orcombinations thereof. In a further aspect, a coating material compriseslow density polyethylene, high density polyethylene, polypropylene,polyester, polytetrafluoroethylene (PTFE), types of polyamide, polyetherether ketone (PEEK), polysulfone, polyvinylidene fluoride (PVDF), poly(4-vinyl pyridine-co-styrene) (PVPCS), polystyrene (PS), polybutadiene,acrylonitrile butadiene styrene (ABS), polyvinyl chloride (PVC),ethylene tetrafluoroethylene polymer (ETFE),poly(chlorotrifluoroethylene) (PCTFE), ethylene chlorotrifluoro ethylene(Halar), polyvinylfluoride (PVF), fluorinated ethylene-propylene (FEP),perfluorinated elastomer, chlorotrifluoroethylenevinylidene fluoride(FKM), perfluoropolyether (PFPE),perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid (NAFION® (copolymerof perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid andtetrafluoroethylene)), polyethylene oxide, polyethylene glycol, sodiumpolyacrylate, polyethylene-block-poly(ethylene glycol),polyacrylonitrile (PAN), polychloroprene (neoprene), polyvinyl butyral(PVB), expanded polystyrene (EPS), polydivinylbenzene, co-polymersthereof, mixtures thereof, or combinations thereof. In a further aspect,a coating material comprises polyvinylidene fluoride (PVDF), polyvinylchloride (PVC), ethylene chlorotrifluoro ethylene (Halar), poly (4-vinylpyridine-co-styrene) (PVPCS), polystyrene (PS), acrylonitrile butadienestyrene (ABS), expanded polystyrene (EPS), polyphenylene sulfide,sulfonated polymer, carboxylated polymer, other polymers, co-polymersthereof, mixtures thereof, or combinations thereof. In a further aspect,a coating is deposited onto an ion exchange particle by dry mixing,mixing in solvent, emulsion, extrusion, bubbling one solvent intoanother, casting, heating, evaporating, vacuum evaporation, spraydrying, vapor deposition, chemical vapor deposition, microwaving,hydrothermal synthesis, polymerization, co-polymerization,cross-linking, irradiation, catalysis, foaming, other depositionmethods, or combinations thereof. In a further aspect, a coating isdeposited using a solvent comprising N-methyl-2-pyrrolidone, dimethylsulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methylethyl ketone, ethanol, acetone, other solvents, or combinations thereof.In a further aspect, a coating is deposited using a solvent comprisingN-methyl-2-pyrrolidone, dimethyl sulfoxide, tetrahydrofuran,dimethylformamide, dimethylacetamide, methyl ethyl ketone, ethanol,acetone, or combinations thereof.

In a further aspect described herein, the coated ion exchange particleshave an average diameter less than about 10 nm, less than about 100 nm,less than about 1,000 nm, less than about 10,000 nm, or less than about100,000 nm. In a further aspect, the coated ion exchange particles havean average size less than about 100 nm, less than about 1,000 nm, orless than about 10,000 nm. In a further aspect, the coated ion exchangeparticles are optionally secondary particles comprised of smallerprimary particles that have an average diameter less than about 10 nm,less than about 100 nm, less than about 1,000 nm, less than about 10,000nm, or less than about 100,000 nm. In a further aspect, the coatingoptionally coats the primary ion exchange particles. In a furtheraspect, the coating optionally coats the secondary ion exchangeparticles. In a further aspect, the coating optionally coats thesecondary ion exchange particles. In a further aspect, the coatingoptionally coats both the primary ion exchange particles and thesecondary ion exchange particles. In a further aspect, the primary ionexchange particles optionally have a first coating and the secondary ionexchange particles optionally have a second coating that is optionallyidentical, similar, or different in composition to the first coating.

In some embodiments described herein, the coating material has athickness less than about 1 nm, less than about 10 nm, less than about100 nm, less than about 1,000 nm, or less than about 10,000 nm. Infurther embodiments, the coating material has a thickness less thanabout 5 nm, less than about 50 nm, or less than about 500 nm. In someembodiments, the ion exchange particles have a coating material with athickness selected from the following list: less than 1 nm, less than 10nm, less than 100 nm, or less than 1,000 nm. In some embodiments, thecoating material has a thickness selected from the following list: lessthan 1 nm, less than 10 nm, or less than 100 nm. In certain embodiments,the coating material has a thickness between about 0.5 nm to about 1000nm. In some embodiments, the coating material has a thickness betweenabout 1 nm to about 100 nm.

In a further aspect described herein, the ion exchange material and thecoating material form one or more concentration gradients where thechemical composition of the particle ranges between two or morecompositions. In a further aspect, the chemical composition optionallyvaries between the ion exchange materials and the coating in a mannerthat is continuous, discontinuous, or continuous and discontinuous indifferent regions of the particle. In a further aspect, the ion exchangematerials and the coating materials form a concentration gradient thatextends over a thickness less than about 1 nm, less than about 10 nm,less than about 100 nm, less than about 1,000 nm, less than about 10,000nm, or less than about 100,000 nm. In a further aspect, the ion exchangematerials and the coating materials form a concentration gradient thatextends over a thickness of about 1 nm to about 1,000 nm.

In a further aspect described herein, the ion exchange material issynthesized by a method such as hydrothermal, solvothermal, sol-gel,solid state, molten salt flux, ion exchange, microwave, ball milling,chemical precipitation, co-precipitation, vapor deposition, orcombinations thereof. In a further aspect, the ion exchange material issynthesized by a method such as chemical precipitation, hydrothermal,solid state, or combinations thereof.

In a further aspect described herein, the coating material is depositedby a method such as chemical vapor deposition, atomic layer deposition,physical vapor deposition, hydrothermal, solvothermal, sol-gel, solidstate, molten salt flux, ion exchange, microwave, chemicalprecipitation, co-precipitation, ball milling, pyrolysis, orcombinations thereof. In a further aspect, the coating material isdeposited by a method such as sol-gel, chemical precipitation, orcombinations thereof. In a further aspect, the coating materials isdeposited in a reactor that is optionally a batch tank reactor, acontinuous tank reactor, a batch furnace, a continuous furnace, a tubefurnace, a rotary tube furnace, or combinations thereof.

In some embodiments, a coating material is deposited with physicalcharacteristics selected from the following list: crystalline,amorphous, full coverage, partial coverage, uniform, non-uniform, orcombinations thereof.

In some embodiments, multiple coatings are optionally deposited on theion exchange material in an arrangement selected from the followinglist: concentric, patchwork, or combinations thereof.

In some embodiments, the matrix is selected from the following list: apolymer, an oxide, a phosphate, or combinations thereof. In someembodiments, a structural support is selected from the following list:polyvinyl fluoride, polyvinylidene fluoride, polyvinyl chloride,polyvinylidene chloride, polyethylene, polypropylene, polyphenylenesulfide, polytetrafluoroethylene, polytetrofluoroethylene, sulfonatedpolytetrofluoroethylene, polystyrene, polydivinylbenzene, polybutadiene,sulfonated polymer, carboxylated polymer, Nafion, copolymers thereof,and combinations thereof. In some embodiments, a structural support isselected from the following list: polyvinylidene difluoride, polyvinylchloride, sulfonated polytetrofluoroethylene, polystyrene,polydivinylbenzene, copolymers thereof, or combinations thereof. In someembodiments, a structural support is selected from the following list:titanium dioxide, zirconium dioxide, silicon dioxide, solid solutionsthereof, or combinations thereof. In some embodiments, the matrixmaterial is selected for thermal resistance, acid resistance, and/orother chemical resistance.

In some embodiments, the porous bead is formed by mixing the ionexchange particles, the matrix material, and the filler materialtogether at once. In some embodiments, the porous bead is formed byfirst mixing the ion exchange particles and the matrix material, andthen mixing with the filler material. In some embodiments, the porousbead is formed by first mixing the ion exchange particles and the fillermaterial, and then mixing with the matrix material. In some embodiments,the porous bead is formed by first mixing the matrix material and thefiller material, and then mixing with the ion exchange particles.

In some embodiments, the porous bead is formed by mixing the ionexchange particles, the matrix material, and/or the filler material witha solvent that dissolves once or more of the components. In someembodiments, the porous bead is formed by mixing the ion exchangeparticles, the matrix material, and/or the filler material as drypowders in a mixer or ball mill. In some embodiments, the porous bead isformed by mixing the ion exchange particles, the matrix material, and/orthe filler material in a spray drier.

In some embodiments, the matrix material is a polymer that is dissolvedand mixed with the ion exchange particles and/or filler material using asolvent from the following list: n-methyl-2-pyrrolidone, dimethylsulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methylethyl ketone, or combinations thereof. In some embodiments, the fillermaterial is a salt that is dissolved and mixed with the ion exchangeparticles and/or matrix material using a solvent from the followinglist: water, ethanol, iso-propyl alcohol, acetone, or combinationsthereof.

In some embodiments, the filler material is a salt that is dissolved outof the bead to form pores using a solution selected from the followinglist: water, ethanol, iso-propyl alcohol, a surfactant mixture, an acida base, or combinations thereof. In some embodiments, the fillermaterial is a material that thermally decomposes to form a gas at hightemperature so that the gas can leave the bead to form pores, where thegas is selected from the following list: water vapor, oxygen, nitrogen,chlorine, carbon dioxide, nitrogen oxides, organic vapors, orcombinations thereof.

In some embodiments, the porous ion exchange bead is formed from drypowder using a mechanical press, a pellet press, a tablet press, a pillpress, a rotary press, or combinations thereof. In some embodiments, theporous ion exchange bead is formed from a solvent slurry by dripping theslurry into a different liquid solution. The solvent slurry isoptionally formed using a solvent of n-methyl-2-pyrrolidone, dimethylsulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methylethyl ketone, or combinations thereof. The different liquid solution isoptionally formed using water, ethanol, iso-propyl alcohol, acetone, orcombinations thereof.

In some embodiments, the porous ion exchange bead is approximatelyspherical with an average diameter selected from the following list:less than 10 um, less than 100 um, less than 1 mm, less than 1 cm, orless than 10 cm. In some embodiments, the porous ion exchange bead isapproximately spherical with an average diameter selected from thefollowing list: less than 200 um, less than 2 mm, or less than 20 mm. Incertain embodiments, the porous ion exchange bead is approximatelyspherical with an average diameter between 10 um and 2 mm.

In some embodiments, the porous ion exchange bead is tablet-shaped witha diameter of less than 1 mm, less than 2 mm, less than 4 mm, less than8 mm, or less than 20 mm and with a height of less than 1 mm, less than2 mm, less than 4 mm, less than 8 mm, or less than 20 mm. In certainembodiments, the porous ion exchange bead is tablet-shaped with adiameter between 500 um and 10 mm.

In some embodiments, the porous ion exchange bead is embedded in asupport structure, which is optionally a membrane, a spiral-woundmembrane, a hollow fiber membrane, or a mesh. In some embodiments, theporous ion exchange bead is embedded on a support structure comprised ofa polymer, a ceramic, or combinations thereof. In some embodiments, theporous ion exchange bead is loaded directly into an ion exchange columnwith no additional support structure.

In some embodiments, the liquid resource is selected from the followinglist: a natural brine, a dissolved salt flat, a geothermal brine,seawater, concentrated seawater, desalination effluent, a concentratedbrine, a processed brine, liquid from an ion exchange process, liquidfrom a solvent extraction process, a synthetic brine, leachate fromores, leachate from minerals, leachate from clays, leachate fromrecycled products, leachate from recycled materials, or combinationsthereof. In some embodiments, a liquid resource is selected from thefollowing list: a natural brine, a dissolved salt flat, a concentratedbrine, a processed brine, a synthetic brine, a geothermal brine, liquidfrom an ion exchange process, liquid from a solvent extraction process,leachate from minerals, leachate from clays, leachate from recycledproducts, leachate from recycled materials, or combinations thereof. Insome embodiments, the liquid resource is optionally pre-treated prior toentering the ion exchange reactor to remove suspended solids,hydrocarbons, or organic molecules. In some embodiments, the liquidresource is optionally enter the ion exchange reactor without anypre-treatment following from its source.

In some embodiments, the liquid resource is selected with a lithiumconcentration selected from the following list: less than 100,000 ppm,less than 10,000 ppm, less than 1,000 ppm, less than 100 ppm, less than10 ppm, or combinations thereof. In some embodiments, a liquid resourceis selected with a lithium concentration selected from the followinglist: less than 5,000 ppm, less than 500 ppm, less than 50 ppm, orcombinations thereof.

Device for Extracting Lithium from a Liquid Resource

In one aspect described herein, is a device for lithium extraction froma liquid resource comprising one or more vessels independentlyconfigured to simultaneously accommodate porous ion exchange beadsmoving in one direction and alternately acid, brine, and optionallyother solutions moving in the net opposite direction.

In one aspect described herein, there is a device for lithium extractionfrom a liquid resource comprising a stirred rank reactor, an ionexchange material, and a pH modulating setup for increasing the pH ofthe liquid resource in the stirred tank reactor.

In one aspect described herein, is a device for lithium extraction froma liquid resource comprising a stirred rank reactor, an ion exchangematerial, a pH modulating setup for increasing the pH of the liquidresource in the stirred tank reactor, and a compartment for containingthe ion exchange material in the stirred tank reactor while allowing forremoval of liquid resource, washing fluid, and acid solutions from thestirred tank reactor.

In one embodiment, at least one of the one or more vessels are fittedwith a conveyer system suitably outfitted to move porous ion exchangebeads upward and simultaneously allow a net flow of acid, brine, andoptionally other solutions, downward. In one embodiment, the conveyorsystem comprises fins with holes. In one embodiment, wherein the finsslide upward over a sliding surface that is fixed in place. In oneembodiment, the fins slide upward over a sliding surface that is fixedin place. In one embodiment, all of the one or more vessels are fittedwith a conveyor system suitably outfitted to move porous ion exchangebeads upward and simultaneously allow a net flow of acid, brine, andoptionally other solutions, downward. In one embodiment, there are aneven number of vessels. In one embodiment, there are an odd number ofvessels. In one embodiment, the vessels are columns.

In some embodiments, structures with holes are used to move the ionexchange material through one or more vessels. In some embodiments, theholes in the structures may be less than 10 microns, less than 100microns, less than 1,000 microns, or less than 10,000 microns. In someembodiments, the structures may be attached to a conveyer system. Insome embodiments, the structures may comprise a porous compartment,porous partition, or other porous structure. In some embodiments, thestructures may contain a bed of fixed or fluidized ion exchangematerial. In some embodiments, the structures may contain ion exchangematerial while allowing brine, aqueous solution, or acid solution topass through the structures.

In one embodiment, the porous ion exchange beads comprise ion exchangeparticles that reversibly exchange lithium and hydrogen and a structuralmatrix material and having a pore network. In one embodiment, the liquidresource comprises a natural brine, a dissolve salt flat, a concentratedbrine, a processed brine, a filtered brine, a liquid from an ionexchange process, a liquid from a solvent extraction process, asynthetic brine, leachate from ores, leachate from minerals, leachatefrom clays, leachate from recycled products, leachate from recycledmaterials, or combinations thereof.

Methods of Modulating pH for the Extraction of Lithium

An aspect of the invention described herein is a method of extractinglithium ions from a liquid resource, comprising: flowing the liquidresource through the column of the system described above to produce alithiated ion exchange material; and treating the resulting lithiatedion exchange material with an acid solution to produce a salt solutioncomprising lithium ions.

An aspect of the invention described herein is a method of extractinglithium ions from a liquid resource, comprising: flowing the liquidresource through the plurality of columns of the system described aboveto produce a lithiated ion exchange material; and treating the resultinglithiated ion exchange material with an acid solution to produce a saltsolution comprising lithium ions.

An aspect of the invention described herein is a method of extractinglithium ions from a liquid resource, comprising: flowing the liquidresource through the tank of the system described above to produce alithiated ion exchange material; and treating the resulting lithiatedion exchange material with an acid solution to produce a salt solutioncomprising lithium ions.

An aspect of the invention described herein is a method of extractinglithium ions from a liquid resource, comprising: flowing the liquidresource through the column of the system described above to produce alithiated ion exchange material; and treating the resulting lithiatedion exchange material with an acid solution to produce a salt solutioncomprising lithium ions.

In some embodiments, the liquid resource is selected from the followinglist: a natural brine, a dissolved salt flat, a geothermal brine,seawater, concentrated seawater, desalination effluent, a concentratedbrine, a processed brine, liquid from an ion exchange process, liquidfrom a solvent extraction process, a synthetic brine, leachate fromores, leachate from minerals, leachate from clays, leachate fromrecycled products, leachate from recycled materials, or combinationsthereof. In some embodiments, a liquid resource is selected from thefollowing list: a natural brine, a dissolved salt flat, a concentratedbrine, a processed brine, a synthetic brine, a geothermal brine, liquidfrom an ion exchange process, liquid from a solvent extraction process,leachate from minerals, leachate from clays, leachate from recycledproducts, leachate from recycled materials, or combinations thereof. Insome embodiments, the liquid resource is optionally pre-treated prior toentering the ion exchange reactor to remove suspended solids,hydrocarbons, or organic molecules. In some embodiments, the liquidresource is optionally entered the ion exchange reactor without anypre-treatment following from its source.

In an embodiment, the liquid resource is a natural brine, a dissolvedsalt flat, seawater, concentrated seawater, a desalination effluent, aconcentrated brine, a processed brine, an oilfield brine, a liquid froman ion exchange process, a liquid from a solvent extraction process, asynthetic brine, a leachate from an ore or combination of ores, aleachate from a mineral or combination of minerals, a leachate from aclay or combination of clays, a leachate from recycled products, aleachate from recycled materials, or combinations thereof.

In some embodiments, the liquid resource is selected with a lithiumconcentration selected from the following list: less than 100,000 ppm,less than 10,000 ppm, less than 1,000 ppm, less than 100 ppm, less than10 ppm, or combinations thereof. In some embodiments, a liquid resourceis selected with a lithium concentration selected from the followinglist: less than 5,000 ppm, less than 500 ppm, less than 50 ppm, orcombinations thereof.

In some embodiments, the acid used for recovering lithium from the ionexchange reactor is selected from the following list: hydrochloric acid,sulfuric acid, phosphoric acid, hydrobromic acid, chloric acid,perchloric acid, nitric acid, formic acid, acetic acid, or combinationsthereof. In some embodiments, the acid used for recovering lithium fromthe porous ion exchange beads is selected from the following list:hydrochloric acid, sulfuric acid, nitric acid, or combinations thereof.

In an embodiment, the acid solution comprises hydrochloric acid,sulfuric acid, phosphoric acid, hydrobromic acid, chloric acid,perchloric acid, nitric acid, formic acid, acetic acid, or combinationsthereof.

In some embodiments, the acid used for recovering lithium from the ionexchange system has a concentration selected from the following list:less than 0.1 M, less than 1.0 M, less than 5 M, less than 10 M, orcombinations thereof. In some embodiments, the acid used for recoveringlithium from the porous ion exchange beads has a concentration greaterthan 10 M.

In an embodiment, acids with distinct concentrations are used during theelution process. In an embodiment, acid with a lower concentration isfirst added to elute lithium from the ion exchange material and thenadditional acid of a greater concentration is added to elute morelithium into the solution and increase the concentration of lithium inthe eluate.

In some embodiments, the ion exchange beads perform the ion exchangereaction repeatedly while maintaining adequate lithium uptake capacityover a number of cycles selected from the following list: greater than10 cycles, greater than 30 cycles, greater than 100 cycles, greater than300 cycles, or greater than 1,000 cycles. In some embodiments, theporous ion exchange beads perform the ion exchange reaction repeatedlyover a number of cycles selected from the following list: greater than50 cycles, greater than 100 cycles, or greater than 200 cycles. In someembodiments, adequate lithium uptake capacity is optionally defined as apercentage of initial uptake capacity selected from the following list:greater than 95%, greater than 90%, greater than 80%, greater than 60%,or greater than 20%. In some embodiments, adequate lithium uptakecapacity is optionally defined as a percentage of initial uptakecapacity such as less than 20%.

In some embodiments, the concentrated lithium solution that is yieldedfrom the ion exchange reactor is further processed into lithium rawmaterials using methods selected from the following list: solventextraction, ion exchange, chemical precipitation, electrodialysis,electrowinning, electrolysis, evaporation with direct solar energy,evaporation with concentrated solar energy, evaporation with a heattransfer medium heated by concentrated solar energy, evaporation withheat from a geothermal brine, evaporation with heat from combustion, pHneutralization, or combinations thereof. In some embodiments, theconcentrated lithium solution that is yielded from the ion exchangereactor is concentrated using reverse osmosis or membrane technologies.

In some embodiments, the concentrated lithium solution that is yieldedfrom the ion exchange reactor is further processed into lithiumchemicals selected from the following list: lithium chloride, lithiumcarbonate, lithium hydroxide, lithium metal, lithium metal oxide,lithium metal phosphate, lithium sulfide, or combinations thereof. Insome embodiments, the concentrated lithium solution that is yielded fromthe porous ion exchange beads is further processed into lithiumchemicals that are solid, liquid, hydrated, or anhydrous.

In some embodiments, the lithium chemicals produced using the ionexchange reactor are used in an industrial application selected from thefollowing list: lithium batteries, metal alloys, glass, grease, orcombinations thereof. In some embodiments, the lithium chemicalsproduced using the coated ion exchange particles are used in anapplication selected from the following list: lithium batteries,lithium-ion batteries, lithium sulfur batteries, lithium solid-statebatteries, and combinations thereof.

In some embodiments, the ion exchange materials are synthesized in alithiated state with a sublattice fully or partly occupied by lithium.In some embodiments, the ion exchange materials are synthesized in ahydrated state with a sublattice fully or partly occupied by hydrogen.

In some embodiments, the ion exchange material extracts lithium ionsfrom a liquid resource. During the extraction of lithium ions from aliquid resource by the ion exchange material, the pH of the liquidresource optionally decreases. Increasing the pH of the liquid resourcein the system by using a pH modulating setup maintains the pH in a rangethat is suitable for lithium ion uptake by the ion exchange material. Inan embodiment, the pH modulating setup comprises measuring the pH of thesystem and adjusting the pH of the system to an ideal pH range forlithium extraction. In an embodiment, for ion exchange material toabsorb lithium from brine, an ideal pH range for the brine is optionally6 to 9, a preferred pH range is optionally 4 to 9, and an acceptable pHrange is optionally 2 to 9. In an embodiment, the pH modulating setupcomprises measuring the pH of the system and wherein the pH of thesystem is less than 6, less than 4, or less than 2, the pH of the systemis adjusted to a pH of 2 to 9, a pH of 4 to 9, or a pH of 6 to 9.

Another aspect described herein is a method of extracting lithium ionsfrom a liquid resource, comprising: a) flowing the liquid resource intoa system comprising a tank to produce a lithiated ion exchange mateiral,wherein the tank further comprises (i) one or more compartments, (ii) anion exchange material, (iii) a mixing device, and (iv) a pH modulatingsetup for changing the pH of the liquid resource in the system; and b)treating the lithiated ion exchange material from a) with an acidsolution to produce a hydrogen-rich ion exchange material and a saltsolution comprising lithium ions.

In some embodiments, the method further comprises, prior to b), washingthe lithiated ion exchange material with an aqueous solution. In someembodiments, the method further comprises, subsequent to b), washing thehydrogen-rich ion exchange material with an aqueous solution. In someembodiments, the aqueous solution is water.

In some embodiments, the method further comprises, prior to b), flowingthe lithiated ion exchange material into a washing system. In someembodiments, the method further comprises, prior to b), transferring asuspension comprising the lithiated ion exchange material. In someembodiments, the method further comprises, prior to b), flowing thelithiated ion exchange material into a washing system and washing thelithiated ion exchange material with a solution. In some embodiments,the method further comprises, prior to b), flowing the lithiated ionexchange material into a washing system and washing the lithiated ionexchange material with a solution comprising water. In some embodiments,the method further comprises, prior to b), flowing the lithiated ionexchange material into a washing system and washing the lithiated ionexchange material with an aqueous solution. In some embodiments, thelithiated ion exchange material is washed with an aqueous solution.

In some embodiments, the method further comprises, prior to b), flowingthe lithiated ion exchange material into a stripping system. In someembodiments, the method further comprises, prior to b), flowing thelithiated ion exchange material into a stripping system and strippingthe lithiated ion exchange material. In some embodiments, the methodfurther comprises, prior to b), flowing the lithiated ion exchangematerial into a stripping system and stripping volatile components fromthe lithiated ion exchange material. In some embodiments, the methodfurther comprises, prior to b), flowing the lithiated ion exchangematerial into a stripping system and stripping volatile componentscomprising water from the lithiated ion exchange material.

In some embodiments, the pH modulating setup comprises a pH measuringdevice and an inlet for adding base to the tank. In some embodiments,the pH measuring device is a pH probe. In some embodiments, the inlet isa pipe. In some embodiments, the inlet is an injection port.

In some embodiments, the method further comprises, during a), measuringa change in pH of the liquid resource using the pH modulating setup. Insome embodiments, the measured change in pH triggers adding a base tomaintain lithium uptake. In some embodiments, a change in pH to below apH value of about 2 to about 9 triggers the addition of a base tomaintain lithium uptake. In some embodiments, a change in pH to below apH value of about 2, of about 3, of about 4, of about 5, of about 6, ofabout 7, of about 8, or of about 9 triggers the addition of a base tomaintain lithium uptake. In some embodiments, a change in pH to below apH of about 2 to about 4, of about 3 to about 5, of about 4 to about 6,of about 5 to about 7, of about 6 to about 8, or of about 7 to about 9triggers the addition of a base to maintain lithium uptake. In someembodiments, base is added to the liquid resource to maintain the pH ofthe liquid resource in a range of about 2-3, 3-4, 4-5, 5-6, 6-7, 7-8, or8-9. In some embodiments, base is added to the liquid resource tomaintain the pH of the liquid resource in a range of about 4-5, 5-6,6-7, or 7-8. In some embodiments, base is added to the liquid resourceto maintain the pH of the liquid resource in a range of about 4.0-4.5,4.5-5.0, 5.0-5.5, 5.5-6.0, 6.0-6.5, 6.5-7.0, 7.0-7.5, or 7.5-8.0. Insome embodiments, the pH of a liquid resource is maintained in a targetrange that is high enough to facilitate lithium uptake and low enough toavoid precipitation of metal salts from the liquid resource. In someembodiments, the pH of a liquid resource is maintained below a pH ofabout 8 to avoid precipitation of Mg salts. In some embodiments, the pHof a liquid resource is maintained below a pH of about 2, below a pH ofabout 3, below a pH of about 4, below a pH of about 5, below a pH ofabout 6, below a pH of about 7, below a pH of about 8, or below a pH ofabout 9 to avoid precipitation of metal salts. In some embodiments, thepH of the liquid resource may drop out of a target pH range due torelease of protons from an ion exchange material and a pH modulatingsetup may adjust the pH of the liquid resource back to within a targetpH range. In some embodiments, the pH of the liquid resource may beadjusted above a target pH range prior to the liquid resource enteringthe system and then protons released from the ion exchange material maydecrease the pH of the system into the target range. In someembodiments, the pH of the liquid resource may be controlled in acertain range and the range may be changed over time. In someembodiments, the pH of the liquid resource may be controlled in acertain range and then the pH of the liquid resource may be allowed todrop. In some embodiments, the pH of the liquid resource may becontrolled in a certain range and then the pH of the liquid resource maybe allowed to drop to solubilize colloids or solids. In someembodiments, base may be added to a liquid resource to neutralizeprotons without measuring pH. In some embodiments, base may be added toa liquid resource to neutralize protons with monitoring of volumes orquantities of the base. In some embodiments, the pH of the liquidresource may be measured to monitor lithium uptake by an ion exchangematerial. In some embodiments, the pH of the liquid resource may bemonitored to determine when to separate a liquid resource from an ionexchange material. In some embodiments, the rate of change of the pH ofthe liquid resource may be measured to monitor the rate of lithiumuptake. In some embodiments, the rate of change of the pH of the liquidresource may be measured to determine when to separate a liquid resourcefrom an ion exchange material.

In some embodiments, the tank further comprises a porous partition. Insome embodiments, the porous partition is a porous polymer partition. Insome embodiments, the porous partition is a mesh or membrane. In someembodiments, the porous partition is a polymer mesh or polymer membrane.In some embodiments, the porous partition comprises one or more layersof mesh, membrane, or other porous structure. In some embodiments, theporous partition comprises one or more coarse meshes that providestructural support and one or more fine meshes and/or membranes thatprovide filtration. In some embodiments, the porous partition comprisesa polyether ether ketone mesh, a polypropylene mesh, a polyethylenemesh, a polysulfone mesh, a polyester mesh, a polyamide mesh, apolytetrafluoroethylene mesh, an ethylene tetrafluoroethylene polymermesh, a stainless steel mesh, a stainless steel mesh coated in polymer,a stainless steel mesh coated in ceramic, or a combination thereof,wherein the mesh is a course mesh, a fine mesh, or a combinationthereof. In some embodiments, the porous polymer partition comprises amesh comprising one or more blends of two or more of a polyether etherketone, a polypropylene, a polyethylene, a polysulfone, a polyester, apolyamide, a polytetrafluoroethylene, or an ethylene tetrafluoroethylenepolymer. In some embodiments, the porous partition comprises a polyetherether ketone membrane, a polypropylene membrane, a polyethylenemembrane, a polysulfone membrane, a polyester membrane, a polyamidemembrane, a polytetrafluoroethylene membrane, an ethylenetetrafluoroethylene polymer membrane, or combinations thereof.

In some embodiments, the method further comprises, after a), drainingthe liquid resource through the porous partition after the production ofthe lithiated ion exchange material.

In some embodiments, the method further comprises, after b), drainingthe salt solution comprising lithium ions through the porous partitionafter the production of the hydrogen-rich ion exchange material.

In some embodiments, the method further comprises, subsequent to a),flowing the lithiated ion exchange material into another systemcomprising a tank to produce the hydrogen-rich ion exchange material andthe salt solution comprising lithium ions, wherein the tank of the othersystem further comprises (i) one or more compartments, and (ii) a mixingdevice.

In some embodiments, the system comprises a plurality of tanks and eachof the plurality of tanks further comprises (i) one or morecompartments, (ii) an ion exchange material, (iii) a mixing device, and(iv) a pH modulating setup for changing the pH of the system.

An aspect described herein is a method of extracting lithium ions from aliquid resource, comprising: a) flowing the liquid resource into a firstsystem comprising a tank, wherein the tank of the first system furthercomprises (i) one or more compartments, (ii) an ion exchange material,(iii) a mixing device, and (iv) a pH modulating setup for changing thepH of the liquid resource in the first system, to produce a lithiatedion exchange material; b) flowing the lithiated ion exchange material ofa) into a second system comprising a tank, wherein the tank of thesecond system further comprises (i) one or more compartments, and (ii) amixing device; and c) treating the lithiated ion exchange from b) withan acid solution to produce a hydrogen-rich ion exchange material and asalt solution comprising lithium ions.

In some embodiments, the method further comprises, subsequent to a),washing the lithiated ion exchange material with an aqueous solution.

In some embodiments, the method further comprises, prior to b), addingan aqueous solution to the lithiated ion exchange material to form afluidized lithiated ion exchange material.

In some embodiments, the method further comprises, subsequent to c),washing the hydrogen-rich ion exchange material with an aqueoussolution. In some embodiments, the aqueous solution is water.

In some embodiments, the pH modulating setup comprises a pH measuringdevice and an inlet for adding base. In some embodiments, the pHmeasuring device is a pH probe. In some embodiments, the inlet is apipe. In some embodiments, the inlet is an injection port.

In some embodiments, the method further comprises, during a), measuringa change in pH of the liquid resource using the pH modulating setup. Insome embodiments, the change in pH triggers adding a base to maintainlithium uptake.

An aspect described herein is a method of extracting lithium ions from aliquid resource, comprising: a) flowing the liquid resource into a firstsystem comprising a plurality of tanks to produce a lithiated ionexchange material, wherein each of the plurality of tanks in the firstsystem is in fluid communication with every other one of the pluralityof tanks in the first system and, each of the plurality of tanks in thefirst system further comprises (i) one or more compartments, (ii) an ionexchange material, (iii) a mixing device, and (iv) a pH modulating setupfor changing the pH of each of the plurality of tanks in the firstsystem; b) flowing the lithiated ion exchange material into a secondsystem comprising a plurality of tanks, wherein each of the plurality oftanks in the second system is in fluid communication with every otherone of the plurality of tanks in the second system and, each of theplurality of tanks in the second system further comprises (i) one ormore compartments, and (ii) a mixing device; and c) treating thelithiated ion exchange material from b) with an acid solution in atleast one of the plurality of tanks in the second system to produce ahydrogen-rich ion exchange material and a salt solution comprisinglithium ions.

In some embodiments, the method further comprises, subsequent to c),washing the hydrogen-rich ion exchange material with an aqueous solutionin at least one of the plurality of tanks in the second system.

In some embodiments, the method is operated in a batch mode. In someembodiments, the method is operated in a continuous mode. In someembodiments, the method is operated in continuous and batch mode. Insome embodiments, the method is operated in continuous mode, a batchmode, a semi-continuous mode, or combinations thereof.

In some embodiments, the pH modulating setup comprises a pH measuringdevice and an inlet for adding base. In some embodiments, the pHmeasuring device is a pH probe. In some embodiments, the inlet is apipe. In some embodiments, the inlet is an injection port.

In some embodiments, the method further comprises, during a), measuringa change in pH of the liquid resource using the pH modulating setup. Insome embodiments, the change in pH triggers adding a base to maintainlithium uptake.

An aspect described herein is a method of extracting lithium ions from aliquid resource, comprising: a) flowing the liquid resource into a firstsystem comprising a tank to produce a lithiated ion exchange material,wherein the tank further comprises (i) one or more compartments, (ii)ion exchange material, and (iii) a mixing device; b) flowing thelithiated ion exchange material from a) into a second system comprisinga tank, wherein the tank further comprises (i) one or more compartments,(ii) an acid solution, and (iii) a mixing device; and c) stripping thelithiated ion exchange material to produce hydrogen-rich ion exchangematerial and a salt solution comprising lithium ions.

In some embodiments, prior to b), the lithiated ion exchange material iswashed. In some embodiments, the lithiated ion exchange material iswashed with an aqueous solution.

An aspect described herein is a method of extracting lithium ions from aliquid resource, comprising: a) providing a system comprising an ionexchange material, a tank comprising one or more compartments; and amixing device, wherein (i) the ion exchange material is oxide-based andexchanges hydrogen ions with lithium ions, and (ii) the mixing device iscapable of moving the liquid resource around the tank comprising one ormore compartments; b) flowing the liquid resource into the system of a),thereby contacting the liquid resource with the ion exchange material,wherein the ion exchange material exchanges hydrogen ions with lithiumions in the liquid resource to produce lithiated ion exchange material;c) removing the liquid resource from the system of b); d) flowing anacid solution into the system of c) thereby contacting the acid solutionwith the lithiated ion exchange material, wherein the lithiated ionexchange material exchanges lithium ions with the hydrogen ions in theacid solution to produce the ion exchange material and a salt solutioncomprising lithium ions from the lithiated ion exchange material; and e)collecting the salt solution comprising the lithium ions for furtherprocessing.

In some embodiments, the salt solution comprising lithium ions undergoescrystallization.

A method of extracting lithium ions from a liquid resource, comprising:a) flowing the liquid resource through a system comprising an ionexchange material and a plurality of columns, wherein the plurality ofcolumns is configured to transport the ion exchange material along thelength of the column, to produce a lithiated ion exchange material; andb) treating the lithiated ion exchange material from a) with an acidsolution to produce a salt solution comprising lithium ions.

An aspect described herein is a method of extracting lithium ions from aliquid resource, comprising: a) providing a system comprising an ionexchange material and a plurality of columns, wherein each of theplurality of columns is configured to transport the ion exchangematerial along the length of the column; b) flowing the liquid resourcethrough a first one of the plurality of columns to produce a lithiatedion exchange material; c) flowing the lithiated ion exchange materialfrom b) into a second one of the plurality of columns; and d) treatingthe lithiated ion exchange material from c) with an acid solution toproduce a hydrogen-rich ion exchange material and a salt solutioncomprising lithium ions.

In some embodiments, the method further comprises, subsequent to b),flowing the lithiated ion exchange material into another one of theplurality of columns and washing the lithiated ion exchange materialwith an aqueous solution. In some embodiments, the method furthercomprises, subsequent to d), flowing the hydrogen-rich ion exchangematerial into another one of the plurality of columns and washing thehydrogen-rich ion exchange material with an aqueous solution.

An aspect described herein is a method of extracting lithium ion from aliquid resource, comprising: a) providing a system comprising an ionexchange material and a plurality of columns, wherein each of theplurality of columns is configured to transport the ion exchangematerial along the length of the column; b) flowing the liquid resourcethrough a first one of the plurality of columns to produce a lithiatedion exchange material; c) flowing the lithiated ion exchange materialfrom b) into a second one of the plurality of columns; d) washing thelithiated ion exchange material from c) with an aqueous solution; e)flowing the lithiated ion exchange material from d) into a third one ofthe plurality of columns; and f) treating the lithiated ion exchangematerial from e) with an acid solution to produce a hydrogen-rich ionexchange material and a salt solution comprising lithium ions.

In some embodiments, the method further comprises: g) flowing thehydrogen-rich ion exchange material into a fourth one of the pluralityof columns; and h) washing the hydrogen-rich ion exchange material withan aqueous solution. In some embodiments, each of the plurality ofcolumns is configured to transport the ion exchange material by a pipesystem or an internal conveyer system. In some embodiments, each of theplurality of columns is configured to transport the ion exchangematerial by a pipe system. In some embodiments, each of the plurality ofcolumns is configured to transport the ion exchange material by aninternal conveyer system.

In some embodiments of the methods described herein, the liquid resourceis a natural brine, a dissolved salt flat, seawater, concentratedseawater, a desalination effluent, a concentrated brine, a processedbrine, waste brine from a bromine-extraction process, an oilfield brine,a liquid from an ion exchange process, a liquid from a solventextraction process, a synthetic brine, a leachate from an ore orcombination of ores, a leachate from a mineral or combination ofminerals, a leachate from a clay or combination of clays, a leachatefrom recycled products, a leachate from recycled materials, orcombinations thereof. In some embodiments of the methods describedherein, the liquid resource is a brine. In some embodiments of themethods described herein, the liquid resource comprises a natural brine,a synthetic brine, or a mixture of a natural and a synthetic brine. Insome embodiments of the methods described herein, the liquid resource isa natural brine, a dissolved salt flat, seawater, concentrated seawater,a desalination effluent, a concentrated brine, a processed brine, wastebrine from a bromine-extraction process, an oilfield brine, a liquidfrom an ion exchange process, or combinations thereof.

In some embodiments of the methods described herein, the acid solutioncomprises hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromicacid, chloric acid, perchloric acid, nitric acid, formic acid, aceticacid, or combinations thereof. In some embodiments of the methodsdescribed herein, the acid solution comprises hydrochloric acid,sulfuric acid, phosphoric acid, nitric acid, or combinations thereof. Insome embodiments of the methods described herein, the acid solutioncomprises hydrochloric acid, sulfuric acid, phosphoric acid, orcombinations thereof. In some embodiments of the methods describedherein the acid solution comprises hydrochloric acid. In someembodiments of the methods described herein the acid solution comprisessulfuric acid. In some embodiments of the methods described herein theacid solution comprises phosphoric acid.

Process of Extracting Lithium from a Liquid Resource

In one aspect described herein, is a process for lithium extraction froma liquid resource comprising treating porous ion exchange beadsalternately with acid, brine, and optionally other solutions, in aconfiguration where the beads move in the net opposite direction to theacid, brine, and optionally other solutions, thereby producing alithium-enriched solution from the liquid resource. In one embodiment,the process comprises: (a) treating the porous ion exchange beads withacid under conditions suitable to absorb hydrogen to generatehydrogen-enriched beads and release lithium to generate alithium-enriched solution; (b) optionally, washing the hydrogen-enrichedbeads with water to generate hydrogen-enriched beads substantially freeof residual acid; (c) treating the hydrogen-enriched beads with theliquid resource under conditions suitable to absorb lithium to generatelithium-enriched beads; (d) optionally, washing the lithium-enrichedbeads with water to generate lithium-enriched beads substantially freeof liquid resource; and (e) repeating the cycle to produce alithium-enriched solution from the liquid resource.

In one aspect described herein, is a process for lithium extraction froma liquid resource comprising treating ion exchange material alternatelywith acid, brine, and optionally other solutions, in a configurationwhere the ion exchange material moves in the net opposite direction tothe acid, brine, and optionally other solutions, thereby producing alithium-enriched solution from the liquid resource. In one aspectdescribed herein, is a process for lithium extraction from a liquidresource comprising treating ion exchange material alternately withacid, the liquid resource, and optionally other solutions, in aconfiguration where the ion exchange material moves in the net oppositedirection to the acid, liquid resource, and optionally other solutions,thereby producing a lithium-enriched solution from the liquid resource.In one aspect described herein, is a process for lithium extraction froma liquid resource comprising treating ion exchange material alternatelywith acid, brine, and optionally other solutions, in a configurationwhere the ion exchange material moves in the net opposite direction tothe acid, brine, and optionally other solutions, thereby producing alithium-enriched solution from the brine. In one embodiment, the processcomprises: (a) treating the ion exchange material with acid underconditions suitable to absorb hydrogen to generate hydrogen-enrichedmaterial and release lithium to generate a lithium-enriched solution;(b) optionally, washing the hydrogen-enriched material with water togenerate hydrogen-enriched material substantially free of residual acid;(c) treating the hydrogen-enriched material with the liquid resourceunder conditions suitable to absorb lithium to generate lithium-enrichedmaterial; (d) optionally, washing the lithium-enriched beads with waterto generate lithium-enriched beads substantially free of liquidresource; and (e) repeating the cycle to produce a lithium-enrichedsolution from the liquid resource.

In one embodiment, the porous ion exchange beads comprise ion exchangeparticles that reversibly exchange lithium and hydrogen and a structuralmatrix material, and having a pore network. In one embodiment, theliquid resource comprises a natural brine, a dissolve salt flat, aconcentrated brine, a processed brine, a filtered brine, a liquid froman ion exchange process, a liquid from a solvent extraction process, asynthetic brine, leachate from ores, leachate from minerals, leachatefrom clays leachate from recycled products, leachate from recycledmaterials, or combinations thereof.

In some embodiments herein, is a process for lithium extraction from aliquid resource comprising treating porous ion exchange beadsalternately with acid, brine, and optionally other solutions, in aconfiguration where the beads move in the net opposite direction to theacid, brine, and optionally other solutions, thereby producing alithium-enriched solution from the liquid resource, wherein the processcomprises: a) treating the porous ion exchange beads with acid underconditions suitable to absorb hydrogen to generate hydrogen-enrichedbeads and release lithium to generate a lithium-enriched solution; b)optionally, washing the hydrogen-enriched beads with water to generatehydrogen-enriched beads substantially free of residual acid; c) treatingthe hydrogen-enriched beads with the liquid resource under conditionssuitable to absorb lithium to generate lithium-enriched beads; d)optionally, washing the lithium-enriched beads with water to generatelithium-enriched beads substantially free of liquid resource; and e)repeating the cycle to produce a lithium-enriched solution from theliquid resource.

In one aspect described herein, is a process for lithium extraction froma liquid resource comprising treating ion exchange particles alternatelywith the liquid resource, washing fluid, and acid, in a system for theextraction of lithium ions from a liquid resource, comprising: a. an ionexchange material; b. a stirred tank reactor; and c. a pH modulatingsetup for increasing the pH of the liquid resource in the system.

In one aspect described herein, is a process for lithium extraction froma liquid resource comprising treating ion exchange particles alternatelywith the liquid resource, a washing fluid, and an acid solution, with asystem for the extraction of lithium ions from a liquid resource,comprising a stirred rank reactor, an ion exchange material, a pHmodulating setup for increasing the pH of the liquid resource in thestirred tank reactor, and a compartment for containing the ion exchangematerial in the stirred tank reactor while allowing for removal ofliquid resource, washing fluid, and acid solutions from the stirred tankreactor.

Process of Modulating pH for the Extraction of Lithium

An aspect of the invention described herein is a process for theextraction of lithium ions from a liquid resource, comprising: a)contacting an ion exchange material with the liquid resource; and b)increasing the pH of the liquid resource before contact with the ionexchange material, during contact with the ion exchange material, aftercontact with the ion exchange material and combinations thereof.

Another aspect described herein is a process for the extraction oflithium ions from a liquid resource, comprising: a) contacting an ionexchange material with the liquid resource; and b) increasing the pH ofthe liquid resource before contact with the ion exchange material,during contact with the ion exchange material, after contact with theion exchange material, or combinations thereof. In some embodiments ofthe process, increasing the pH of the liquid resource is beforecontacting the ion exchange material with the liquid resource. In someembodiments of the process, increasing the pH of the liquid resource isduring contacting the ion exchange material with the liquid resource. Insome embodiments of the process, increasing the pH of the liquidresource is after contacting the ion exchange material with the liquidresource. In some embodiments of the process, increasing the pH of theliquid resource is before and during contacting the ion exchangematerial with the liquid resource. In some embodiments of the process,increasing the pH of the liquid resource is before and after contactingthe ion exchange material with the liquid resource. In some embodimentsof the process, increasing the pH of the liquid resource is during andafter contacting the ion exchange material with the liquid resource. Insome embodiments of the process, increasing the pH of the liquidresource is before, during, and after contacting the ion exchangematerial with the liquid resource.

An aspect of the invention described herein is a process, wherein theion exchange material is loaded into a column. In an embodiment, theprocess further comprises: a) loading a liquid resource into one or moreliquid resource tanks; b) connecting the column to the one or moreliquid resource tanks; and c) passing the liquid resource from the oneor more liquid resource tanks through the column, wherein the passing ofthe liquid resource occurs at least once. In an embodiment, the processfurther comprises increasing the pH of the liquid resource in one ormore pH increasing tanks. In an embodiment, the process furthercomprises settling precipitates in one or more settling tanks. In anembodiment, the process further comprises storing the liquid resource inone or more storing tanks prior to or after circulating the liquidresource through the column.

An aspect of the invention described herein is a process, wherein theprocess further comprises: a) loading the liquid resource into one ormore liquid resource tanks; b) connecting the column to the one or moreliquid resource tanks; c) passing the liquid resource from the one ormore liquid resource tanks through the column, wherein the passing ofthe liquid resource occurs at least once; d) increasing the pH of theliquid resulting from c. in one or more pH increasing tanks; e) settlingprecipitates of the liquid resulting from d. in one or more settlingtanks; and f) storing the liquid resulting from e. in one or morestoring tanks.

An aspect of the invention described herein is a process, wherein theion exchange material is loaded in a plurality of columns. In anembodiment, a plurality of tanks is connected to the plurality ofcolumns, wherein each of the plurality of tanks is immediately connectedto one of the plurality of columns. In an embodiment, two or more of theplurality of columns forms at least one circuit. In an embodiment, atleast one circuit is selected from a liquid resource circuit, a waterwashing circuit and an acid solution circuit. In an embodiment, the pHof the liquid resource is increased in the plurality of tanks connectedto the plurality of columns in the liquid resource circuit. In anembodiment, the liquid resource circuit includes a plurality of columnsconnected to a plurality of tanks, wherein each of the plurality oftanks is immediately connected to one of the plurality of columns.

An aspect of the invention described herein is a process, wherein theprocess further comprises: a) passing the liquid resource through aplurality of columns in the liquid resource circuit; b) passing an acidsolution through a plurality of columns in the acid solution circuit oneor more times; and c) passing water through a plurality of columns inthe water washing circuit. In an embodiment, the process furthercomprises interchanging a plurality of columns between the liquidresource circuit, the water washing circuit and the acid solutioncircuit, such that: a) at least one of the plurality of columns in theliquid resource circuit becomes at least one of the plurality of columnsin the water washing circuit and/or at least one of the plurality ofcolumns in the acid solution circuit; b) at least one of the pluralityof columns in the water washing circuit becomes at least one of theplurality of columns in the acid solution circuit and/or at least one ofthe plurality of columns in the liquid resource circuit; and/or c) atleast one of the plurality of columns in the acid solution circuitbecomes at least one of the plurality of columns in the liquid resourcecircuit and/or at least one of the plurality of columns in the waterwashing circuit.

An aspect of the invention described herein is a process, wherein theion exchange material is loaded into one or more compartments in a tank.In an embodiment, the process further comprises moving the liquidresource through the one or more compartments in the tank. In anembodiment, the tank comprises injection ports. In an embodiment, theprocess further comprises using the injection ports to increase the pHof the liquid resource before contact with the ion exchange material,during contact with the ion exchange material, after contact with theion exchange material and combinations thereof.

In some embodiments, the process further comprises using the injectionports to increase the pH of the liquid resource before contact with theion exchange material, during contact with the ion exchange material,after contact with the ion exchange material, or combinations thereof.

An aspect of the invention described herein is a process, wherein thecolumn further comprises a plurality of injection ports. In anembodiment, the process further comprises using the plurality ofinjection ports to increase the pH of the liquid resource before contactwith the ion exchange material, during contact with the ion exchangematerial, after contact with the ion exchange material and combinationsthereof.

In some embodiments, the process further comprises using the pluralityof injection ports to increase the pH of the liquid resource beforecontact with the ion exchange material, during contact with the ionexchange material, after contact with the ion exchange material, orcombinations thereof.

In an embodiment, the ion exchange material comprises a plurality of ionexchange particles. In an embodiment, the plurality of ion exchangeparticles in the ion exchange material is selected from uncoated ionexchange particles, coated ion exchange particles and combinationsthereof. In an embodiment, the ion exchange material is a porous ionexchange material. In an embodiment, the porous ion exchange materialcomprises a network of pores that allows liquids to move quickly fromthe surface of the porous ion exchange material to the plurality of ionexchange particles. In an embodiment, the ion exchange material is inthe form of porous ion exchange beads.

In an embodiment, the ion exchange material extracts lithium ions from aliquid resource. During the extraction of lithium ions from a liquidresource by the ion exchange material, the pH of the liquid resourceoptionally decreases. Increasing the pH of the liquid resource in thesystem maintains the pH in a range that is suitable for lithium ionuptake by the ion exchange material. In an embodiment, increasing the pHcomprises measuring the pH of the system and adjusting the pH of thesystem to an ideal pH range for lithium extraction. In an embodiment,for ion exchange material to absorb lithium from brine, an ideal pHrange for the brine is optionally 6 to 9, a preferred pH range isoptionally 4 to 9, and an acceptable pH range is optionally 2 to 9. Inan embodiment, increasing the pH comprises measuring the pH of thesystem and wherein the pH of the system is less than 6, less than 4, orless than 2, the pH of the system is adjusted to a pH of 2 to 9, a pH of4 to 9, or a pH of 6 to 9.

Continuous Process for Lithium Extraction

Lithium is an essential element for batteries and other technologies.Lithium is found in a variety of liquid resources, including natural andsynthetic brines and leachate solutions from minerals, clays, andrecycled products. Lithium can be extracted from such liquid resourcesusing an ion exchange process based on inorganic ion exchange materials.These inorganic ion exchange materials absorb lithium from a liquidresource while releasing hydrogen, and then elute lithium in acid whileabsorbing hydrogen. This ion exchange process can be repeated to extractlithium from a liquid resource and yield a concentrated lithiumsolution. The concentrated lithium solution can be further processedinto chemicals for the battery industry or other industries.

Ion exchange materials can be formed into beads and the beads can beloaded into ion exchange columns for lithium extraction. In an ionexchange column with a fixed bed, the beads at one end of the columnapproach saturation quickly, while the beads at the other end of thecolumn never approach saturation. This saturation can be with lithiumduring brine flow or with hydrogen during acid flow. When a bead at thetop of a fixed bed becomes saturated, it must remain in place until theentire column has been adequately saturated. While a bead remains inplace after approaching saturation, it is not able to contributesubstantial absorption capacity to the column. In this situation, theuse of beads in the ion exchange columns is inefficient because thesaturated beads must wait additional time prior to the next processingstep. Furthermore, due to this time waiting period, the beads areexposed to longer flows of acid and brine solutions, which acceleratetheir dissolution and degradation.

The present invention is a continuous process for lithium extractionusing columns with moving beds of ion exchange beads. Multiple columnsmay be used in this process. In one column, acid is pumped through thecolumn and the beads are moved through the column in the oppositedirection as the acid. During this acid flow, the beads absorb hydrogenfrom the acid while releasing lithium. Optionally, in another column,the beads are washed with water to remove the residual acid. In anothercolumn, brine is pumped through the column and the beads are movedthrough the column in the opposite direction as the brine. During thisbrine flow, the beads absorb lithium from the brine while releasinghydrogen. The hydrogen can be neutralized by adding base before, during,or after the brine flow through the column. Optionally, in anothercolumn, the beads are washed with water to remove the residual brine.Then, the beads are returned to the acid column, and the cycle repeats.FIG. 9 illustrates a continuous column with a moving bed of ion exchangebeads. FIG. 10 illustrates an assembly of continuous columns includingtwo types of ion exchange columns for brine and acid flows. FIG. 11illustrates an assembly of continuous columns including two types of ionexchange columns for brine and acid flows, and two types of waterwashing columns for washing residual brine and acid. FIG. 12 illustratean assembly of columns, wherein individual columns can process variousflow rates of liquid solutions and beads with various residence timesand column heights.

Ion exchange materials are typically small particles, which togetherconstitute a fine powder. Small particle size is required to minimizethe diffusion distance that lithium must travel into the core of the ionexchange particles. In some cases, these particles may be coated withprotective surface coatings to minimize dissolution of the ion exchangematerials while allowing efficient transfer of lithium and hydrogen toand from the particles, as disclosed in co-pending U.S. provisionalapplication 62/421,934, filed on Nov. 14, 2016, entitled “LithiumExtraction with Coated Ion Exchange Particles,” and incorporated in itsentirety by reference.

One major challenge for lithium extraction using inorganic ion exchangeparticles is the loading of the particles into an ion exchange column insuch a way that brine and acid can be pumped efficiently through thecolumn with minimal clogging. The materials can be formed into beads,and the beads can be loaded into the column. This bead loading createsvoid spaces between the beads, and these void spaces facilitate pumpingthrough the column. The beads hold the ion exchange particles in placeand prevent free movement of the particles throughout the column. Whenthe materials are formed into beads, the penetration of brine and acidsolutions into the beads may become slow and challenging. A slow rate ofconvection and diffusion of the acid and brine solutions into the beadslows the kinetics of lithium absorption and release. Such slow kineticscan create problems for column operation. Slow kinetics can require slowpumping rates through the column. Slow kinetics can also lead to lowlithium recovery from the brine and inefficient use of acid to elute thelithium.

In some embodiments, the ion exchange beads are porous ion exchangebeads with networks of pores that facilitate the transport into thebeads of solutions that are pumped through an ion exchange column. Porenetworks can be strategically controlled to provide fast and distributedaccess for the brine and acid solutions to penetrate into the bead anddeliver lithium and hydrogen to the ion exchange particles. One exampleof a porous ion exchange bead is shown in FIG. 15.

In some embodiments, the ion exchange beads are formed by mixing of ionexchange particles, a matrix material, and a filler material. Thesecomponents are mixed and formed into a bead. Then, the filler materialis removed from the bead to leave behind pores. The filler material isdispersed in the bead in such a way to leave behind a pore structurethat enables transport of lithium and hydrogen with fast kinetics. Thismethod may involve multiple ion exchange materials, multiple polymermaterials, and multiple filler materials.

Another major challenge for lithium extraction using inorganic ionexchange materials is dissolution and degradation of the materials,especially during lithium elution in acid but also during lithium uptakein liquid resources. To yield a concentrated lithium solution from theion exchange process, it is desirable to use a concentrated acidsolution to elute the lithium. However, concentrated acid solutionsdissolve and degrade inorganic ion exchange materials, which decreasesthe performance and lifespan of the materials. Therefore, the porous ionexchange beads may contain coated ion exchange particle for lithiumextraction that are comprised of an ion exchange material and a coatingmaterial protecting the particle surface. The coating protects the ionexchange material from dissolution and degradation during lithiumelution in acid, during lithium uptake from a liquid resource, andduring other aspects of an ion exchange process. This coated particleenables the use of concentrated acids in the ion exchange process toyield concentrated lithium solutions.

In one aspect described herein, the ion exchange material is selectedfor high lithium absorption capacity, high selectivity for lithium in aliquid resource relative to other ions such as sodium and magnesium,strong lithium uptake in liquid resources including those with lowconcentrations of lithium, facile elution of lithium with a small excessof acid, and fast ionic diffusion. In one aspect described herein, acoating material is selected to protect the particle from dissolutionand chemical degradation during lithium recovery in acid and also duringlithium uptake in various liquid resources. In some embodiments, thecoating material may also be selected to facilitate one or more of thefollowing objectives: diffusion of lithium and hydrogen between theparticles and the liquid resources, enabling adherence of the particlesto a structural support, and suppressing structural and mechanicaldegradation of the particles.

In some embodiments, the continuous ion exchange column may be loadedwith beads at the top and then moved through the ion exchange from topto bottom. In some embodiments, the continuous ion exchange column maybe loaded with beads at the bottom and then moved through the ionexchange from bottom to top. In some embodiments, the continuous ionexchange column may be loaded with beads at the bottom of the column byusing a pipe or conveyer system which is flooded with solution at thebottom but extends upward to a height exceeding the height of thesolution in the ion exchange column. This pipe or conveyer system allowsbeads to be fed into the bottom of the ion exchange column where theyare submerged with liquid solution, while eliminating leakage of theliquid solution out of the column. In some embodiments, the beads areion exchange particles, ion exchange particles with a coating, ionexchange particles without a coating, ion exchange particles embedded ina porous matrix, or combinations thereof. In some embodiments, acontinuous ion exchange column is loaded with ion exchange material atthe top or bottom of the column and the material is removed from thebottom or top of the column. In some embodiments, a continuous ionexchange column is loaded with ion exchange material at the top of thecolumn and the ion exchange material is removed from the bottom of thecolumn. In some embodiments, a continuous ion exchange column is loadedwith ion exchange material at the bottom of the column and the ionexchange material is removed from the top of the column.

In some embodiments, the continuous columns use an internal conveyersystem to move the beads through the column from bottom to top or fromtop to bottom. In some embodiments, the continuous columns use acorkscrew mechanism to move the beads through the column from bottom totop or from top to bottom. In some embodiments, the continuous columnsuse a corkscrew mechanism which slides under the beads while pressingthem upwards. In some embodiments, the continuous columns use acorkscrew mechanism which rotates the beads upwards using friction orstructures on the corkscrew that form ribs, notches, steps, flaps,supports, or fins. These structures may be rigid or flexible, and theymay be made of material that is metal, plastic, or ceramic. The materialchosen for the acid column is acid resistant. In some embodiments,gravity is used to move ion exchange material through a column from topto bottom. In some embodiments, liquid is flowed upward through a columnwhile ion exchange material moves downward in the column or is suspendedin the column by gravity. In some embodiments, the rate that liquid ispumped upward through the column is controlled to suspend the ionexchange material in the column. In some embodiments, the ion exchangematerial in a column is comprised of particles, uncoated particles,coated particles, porous material, porous beads, or porous beadscomprising a structural matrix. In some embodiments, the ion exchangematerial is transported from one column to another column using a pipe,a conveyer, a hopper, a container, a funnel, an elevator, orcombinations thereof. In some embodiments, the column may becylindrical, conical, rectangular, pyramidal, non-cylindrical, orcombinations thereof.

In some embodiments, the continuous columns are hollow cylindersoriented vertically with vertical flows of liquid solutions and beads inopposite directions. In some embodiments, the continuous columns areoriented horizontally with horizontal flows of liquid solutions andbeads in opposite directions. In some embodiments, the continuouscolumns are oriented diagonally upwards with a stepped conveyer system.In some embodiments, the liquid solutions and beads may sometimes flowin the same direction through the columns.

In some embodiments, each column is a conveyer system which may not becylindrical or fully enclosed. In some embodiments, the column is anescalator system where the beads are transported upward while the liquidsolution flows down through the beads. The escalator has a conveyer beltwith fins. The fins have holes to allow the brine to flow downwardthrough the fins. The fins move upward, moving the beads from the bottomto the top. This escalator system with fins attached to a movingconveyer belt is illustrated in FIG. 13.

In some embodiments, each column is a non-cylindrical escalator systemwith fins that move upwards over a smooth sliding surface, which isfixed in position. The fins are not attached to the sliding surface butare rather attached to a separate conveyer system. These fins have holesto allow liquid solutions to flow downward, and the fins move the beadsupward from bottom to top of the conveyer system. This allows the beadsto be saturated by the liquid flow and then removed at the top of theconveyer system. This escalator system with a fixed sliding surface andseparately-mounted fins is illustrated in FIG. 14.

In some embodiments, the holes on the fins may be less than 0.5 mm, lessthan 1 mm, less than 2 mm, less than 4 mm, less than 8 mm, less than 16mm, or less than 32 mm. In some embodiments, a continuous process mayuse conveyer systems that move at different speeds for brine, acid, andother liquid flows. In some embodiments, a continuous process may useconveyer systems with fins of different sizes for brine, acid, or otherliquid solution flows.

When the porous ion exchange beads are used in an ion exchange column,the liquid resource containing lithium is pumped through the ionexchange column so that the ion exchange particles absorb lithium fromthe liquid resource while releasing hydrogen. After the beads haveabsorbed lithium, an acid solution is pumped through the column so thatthe particles release lithium into the acid solution while absorbinghydrogen. The column may be operated in co-flow mode with the liquidresource and acid solution alternately flowing through the column in thesame direction, or the column may be operated in counter-flow mode witha liquid resource and acid solution alternately flowing through thecolumn in opposite directions. Between flows of the liquid resource andthe acid solution, the column may be treated or washed with water orother solutions for purposes such as adjusting pH in the column orremoving potential contaminants. The beads may form a fixed or movingbed, and the moving bed may move in counter-current to the brine andacid flows. The beads may be moved between multiple columns with movingbeds where different columns are used for brine, acid, water, or otherflows. Before or after the liquid resource flows through the column, thepH of the liquid may be adjusted with NaOH or other chemicals tofacilitate the ion exchange reaction as well as handling or disposal ofthe spent liquid resource. Before or after the liquid resource flowsthrough the column, the liquid resource may be subjected to otherprocesses including other ion exchange processes, solvent extraction,evaporation, chemical treatment, or precipitation to remove lithium, toremove other chemical species, or to otherwise treat the brine.

When the ion exchange particles are treated with acid, a lithiumsolution is produced. This lithium solution may be further processed toproduce lithium chemicals. These lithium chemicals may be supplied foran industrial application.

In some embodiments, an ion exchange material is selected from thefollowing list: an oxide, a phosphate, an oxyfluoride, afluorophosphate, or combinations thereof. In some embodiments, an ionexchange material is selected from the following list: Li₄Mn₅O₁₂,Li₄Ti₅O₁₂, Li₂MO₃ (M=Ti, Mn, Sn), LiMn₂O₄, Li_(1.6)Mn1.6O4, LiMO₂ (M=Al,Cu, Ti), Li₄TiO₄, Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄,Li₂CuP₂O₇, Al(OH)₃, LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O,TiO₂.xSb₂O₅.yH₂O, solid solutions thereof, or combinations thereof. Insome embodiments, an ion exchange material is selected from thefollowing list: Li₄Mn₅O₁₂, Li₄Ti₅O₁₂, Li_(1.6)Mn1.6O4, Li₂MO₃ (M=Ti, Mn,Sn), LiFePO4, solid solutions thereof, or combinations thereof.

In some embodiments, a coating material for protecting the surface ofthe ion exchange material is selected from the following list: acarbide, a nitride, an oxide, a phosphate, a fluoride, a polymer,carbon, a carbonaceous material, or combinations thereof. In someembodiments, a coating material is selected from the following list:TiO₂, ZrO₂, MoO₂, SnO₂, Nb₂O₅, Ta₂O₅, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂SiO₃,Li₂MnO₃, Li₂MoO₃, LiNbO₃, LiTaO₃, AlPO₄, LaPO₄, ZrP₂O₇, MoP₂O₇,Mo₂P₃O₁₂, BaSO₄, AlF₃, SiC, TiC, ZrC, Si₃N₄, ZrN, BN, carbon, graphiticcarbon, amorphous carbon, hard carbon, diamond-like carbon, solidsolutions thereof, or combinations thereof. In some embodiments, acoating material is selected from the following list: TiO₂, ZrO₂, MoO₂,SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂SiO₃, Li₂MnO₃, LiNbO₃, AlF₃, SiC, Si₃N₄,graphitic carbon, amorphous carbon, diamond-like carbon, or combinationsthereof.

In some embodiments, the ion exchange particles may have an averagediameter that is selected from the following list: less than 10 nm, lessthan 100 nm, less than 1,000 nm, less than 10,000 nm, or less than100,000 nm. In some embodiments, the ion exchange particles may have anaverage size that is selected from the following list: less than 200 nm,less than 2,000 nm, or less than 20,000 nm.

In some embodiments, the ion exchange particles may be secondaryparticles comprised of smaller primary particles that may have anaverage diameter selected from the following list: less than 10 nm, lessthan 100 nm, less than 1,000 nm, or less than 10,000 nm.

In some embodiments, the ion exchange particles have a coating materialwith a thickness selected from the following list: less than 1 nm, lessthan 10 nm, less than 100 nm, or less than 1,000 nm. In someembodiments, the coating material has a thickness selected from thefollowing list: less than 1 nm, less than 10 nm, or less than 100 nm.

In some embodiments, the ion exchange material and a coating materialmay form one or more concentration gradients where the chemicalcomposition of the particle ranges between two or more compositions. Insome embodiments, the ion exchange materials and the coating materialsmay form a concentration gradient that extends over a thickness selectedfrom the following list: less than 1 nm, less than 10 nm, less than 100nm, less than 1,000 nm, less than 10,000 nm, or less than 100,000 nm.

In some embodiments, the ion exchange material is synthesized by amethod selected from the following list: hydrothermal, solvothermal,sol-gel, solid state, molten salt flux, ion exchange, microwave, ballmilling, precipitation, or vapor deposition. In some embodiments, theion exchange material is synthesized by a method selected from thefollowing list: hydrothermal, solid state, or microwave.

In some embodiments, a coating material is deposited by a methodselected from the following list: chemical vapor deposition, atomiclayer deposition, physical vapor deposition, hydrothermal, solvothermal,sol-gel, solid state, molten salt flux, ion exchange, microwave, wetimpregnation, precipitation, titration, aging, ball milling, orcombinations thereof. In some embodiments, the coating material isdeposited by a method selected from the following list: chemical vapordeposition, hydrothermal, titration, solvothermal, wet impregnation,sol-gel, precipitation, microwave, or combinations thereof.

In some embodiments, a coating material is deposited with physicalcharacteristics selected from the following list: crystalline,amorphous, full coverage, partial coverage, uniform, non-uniform, orcombinations thereof.

In some embodiments, multiple coatings may be deposited on the ionexchange material in an arrangement selected from the following list:concentric, patchwork, or combinations thereof.

In some embodiments, the matrix is selected from the following list: apolymer, an oxide, a phosphate, or combinations thereof. In someembodiments, a structural support is selected from the following list:polyvinyl fluoride, polyvinylidene difluoride, polyvinyl chloride,polyvinylidene dichloride, polyethylene, polypropylene, polyphenylenesulfide, polytetrafluoroethylene, polytetrofluoroethylene, sulfonatedpolytetrofluoroethylene, polystyrene, polydivinylbenzene, polybutadiene,sulfonated polymer, carboxylated polymer, Nafion, copolymers thereof,and combinations thereof. In some embodiments, a structural support isselected from the following list: polyvinylidene difluoride, polyvinylchloride, sulfonated polytetrofluoroethylene, polystyrene,polydivinylbenzene, copolymers thereof, or combinations thereof. In someembodiments, a structural support is selected from the following list:titanium dioxide, zirconium dioxide, silicon dioxide, solid solutionsthereof, or combinations thereof. In some embodiments, the matrixmaterial is selected for thermal resistance, acid resistance, and/orother chemical resistance.

In some embodiments, the porous bead is formed by mixing the ionexchange particles, the matrix material, and the filler materialtogether at once. In some embodiments, the porous bead is formed byfirst mixing the ion exchange particles and the matrix material, andthen mixing with the filler material. In some embodiments, the porousbead is formed by first mixing the ion exchange particles and the fillermaterial, and then mixing with the matrix material. In some embodiments,the porous bead is formed by first mixing the matrix material and thefiller material, and then mixing with the ion exchange particles.

In some embodiments, the porous bead is formed by mixing the ionexchange particles, the matrix material, and/or the filler material witha solvent that dissolves once or more of the components. In someembodiments, the porous bead is formed by mixing the ion exchangeparticles, the matrix material, and/or the filler material as drypowders in a mixer or ball mill. In some embodiments, the porous bead isformed by mixing the ion exchange particles, the matrix material, and/orthe filler material in a spray drier.

In some embodiments, the matrix material is a polymer that is dissolvedand mixed with the ion exchange particles and/or filler material using asolvent from the following list: n-methyl-2-pyrrolidone, dimethylsulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methylethyl ketone, or combinations thereof. In some embodiments, the fillermaterial is a salt that is dissolved and mixed with the ion exchangeparticles and/or matrix material using a solvent from the followinglist: water, ethanol, iso-propyl alcohol, acetone, or combinationsthereof.

In some embodiments, the filler material is a salt that is dissolved outof the bead to form pores using a solution selected from the followinglist: water, ethanol, iso-propyl alcohol, a surfactant mixture, an acida base, or combinations thereof. In some embodiments, the fillermaterial is a material that thermally decomposes to form a gas at hightemperature so that the gas can leave the bead to form pores, where thegas is selected from the following list: water vapor, oxygen, nitrogen,chlorine, carbon dioxide, nitrogen oxides, organic vapors, orcombinations thereof.

In some embodiments, the porous ion exchange bead is formed from drypowder using a mechanical press, a pellet press, a tablet press, a pillpress, a rotary press, or combinations thereof. In some embodiments, theporous ion exchange bead is formed from a solvent slurry by dripping theslurry into a different liquid solution. The solvent slurry may beformed using a solvent of n-methyl-2-pyrrolidone, dimethyl sulfoxide,tetrahydrofuran, dimethylformamide, dimethylacetamide, methyl ethylketone, or combinations thereof. The different liquid solution may beformed using water, ethanol, iso-propyl alcohol, acetone, orcombinations thereof.

In some embodiments, the porous ion exchange bead is approximatelyspherical with an average diameter selected from the following list:less than 10 um, less than 100 um, less than 1 mm, less than 1 cm, orless than 10 cm. In some embodiments, the porous ion exchange bead isapproximately spherical with an average diameter selected from thefollowing list: less than 200 um, less than 2 mm, or less than 20 mm.

In some embodiments, the porous ion exchange bead is tablet-shaped witha diameter of less than 1 mm, less than 2 mm, less than 4 mm, less than8 mm, or less than 20 mm and with a height of less than 1 mm, less than2 mm, less than 4 mm, less than 8 mm, or less than 20 mm.

In some embodiments, the porous ion exchange bead is embedded in asupport structure, which may be a membrane, a spiral-wound membrane, ahollow fiber membrane, or a mesh. In some embodiments, the porous ionexchange bead is embedded on a support structure comprised of a polymer,a ceramic, or combinations thereof. In some embodiments, the porous ionexchange bead is loaded directly into an ion exchange column with noadditional support structure.

In some embodiments, the liquid resource is selected from the followinglist: a natural brine, a dissolved salt flat, a geothermal brine,seawater, concentrated seawater, desalination effluent, a concentratedbrine, a processed brine, liquid from an ion exchange process, liquidfrom a solvent extraction process, a synthetic brine, leachate fromores, leachate from minerals, leachate from clays, leachate fromrecycled products, leachate from recycled materials, or combinationsthereof. In some embodiments, a liquid resource is selected from thefollowing list: a natural brine, a dissolved salt flat, a concentratedbrine, a processed brine, a synthetic brine, a geothermal brine, liquidfrom an ion exchange process, liquid from a solvent extraction process,leachate from minerals, leachate from clays, leachate from recycledproducts, leachate from recycled materials, or combinations thereof.

In some embodiments, the liquid resource is selected with a lithiumconcentration selected from the following list: less than 100,000 ppm,less than 10,000 ppm, less than 1,000 ppm, less than 100 ppm, less than10 ppm, or combinations thereof. In some embodiments, a liquid resourceis selected with a lithium concentration selected from the followinglist: less than 5,000 ppm, less than 500 ppm, less than 50 ppm, orcombinations thereof.

In some embodiments, the acid used for recovering lithium from theporous ion exchange beads is selected from the following list:hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid,chloric acid, perchloric acid, nitric acid, formic acid, acetic acid, orcombinations thereof. In some embodiments, the acid used for recoveringlithium from the porous ion exchange beads is selected from thefollowing list: hydrochloric acid, sulfuric acid, nitric acid, orcombinations thereof.

In some embodiments, the acid used for recovering lithium from theporous ion exchange beads has a concentration selected from thefollowing list: less than 0.1 M, less than 1.0 M, less than 5 M, lessthan 10 M, or combinations thereof.

In some embodiments, the porous ion exchange beads perform the ionexchange reaction repeatedly over a number of cycles selected from thefollowing list: greater than 10 cycles, greater than 30 cycles, greaterthan 100 cycles, greater than 300 cycles, or greater than 1,000 cycles.In some embodiments, the porous ion exchange beads perform the ionexchange reaction repeatedly over a number of cycles selected from thefollowing list: greater than 50 cycles, greater than 100 cycles, orgreater than 200 cycles.

In some embodiments, the concentrated lithium solution that is yieldedfrom the porous ion exchange beads is further processed into lithium rawmaterials using methods selected from the following list: solventextraction, ion exchange, chemical precipitation, electrodialysis,electrowinning, evaporation with direct solar energy, evaporation withconcentrated solar energy, evaporation with a heat transfer mediumheated by concentrated solar energy, evaporation with heat from ageothermal brine, evaporation with heat from combustion, or combinationsthereof.

In some embodiments, the concentrated lithium solution that is yieldedfrom the porous ion exchange beads is further processed into lithiumchemicals selected from the following list: lithium chloride, lithiumcarbonate, lithium hydroxide, lithium metal, lithium metal oxide,lithium metal phosphate, lithium sulfide, or combinations thereof. Insome embodiments, the concentrated lithium solution that is yielded fromthe porous ion exchange beads is further processed into lithiumchemicals that are solid, liquid, hydrated, or anhydrous.

In some embodiments, the lithium chemicals produced using the porous ionexchange beads are used in an industrial application selected from thefollowing list: lithium batteries, metal alloys, glass, grease, orcombinations thereof. In some embodiments, the lithium chemicalsproduced using the coated ion exchange particles are used in anapplication selected from the following list: lithium batteries,lithium-ion batteries, lithium sulfur batteries, lithium solid-statebatteries, and combinations thereof.

In some embodiments, the ion exchange materials are synthesized in alithiated state with a sublattice fully or partly occupied by lithium.In some embodiments, the ion exchange materials are synthesized in ahydrated state with a sublattice fully or partly occupied by hydrogen.

EXAMPLES Example 1 Lithium Extraction Using Coated Ion ExchangeParticles

Lithium is extracted from a brine using coated ion exchange particles.The brine is an aqueous solution containing 50,000 ppm Na and 1,000 ppmLi. The coated ion exchange particles are comprised of an ion exchangematerial and a coating material. The ion exchange material is Li₄Mn₅O₁₂and the coating material is ZrO₂. The particles are comprised of 98 wt.% active material and 2 wt. % of the coating. The particles have a meandiameter of 1.0 microns, and the coating thickness is approximately 2nm.

The particles are created by first synthesizing Li₄Mn₅O₁₂ and thendepositing the coating on the surface of the Li₄Mn₅O₁₂. The particlesare treated with HCl acid to yield LiCl in solution. During acidtreatment, the particles absorb hydrogen while releasing lithium. TheLi₄Mn₅O₁₂ active material is converted to a hydrated state with ahydrogen-rich composition. The ZrO₂ coating allows diffusion of hydrogenand lithium respectively to and from the active material while providinga protective barrier that limits dissolution of manganese and oxygenfrom the active material. The solution is collected for elementalanalysis to measure lithium yield.

After treatment in acid, the hydrated particles are treated with brinewherein the particles absorb lithium while releasing hydrogen. Theparticles are converted from a hydrated state to a lithiated state witha lithium-rich composition. The solution is collected for elementalanalysis to measure lithium uptake.

The lithiated material is then treated again with acid to yield lithiumin solution as described previously. The cycle of hydration andlithiation is repeated to extract lithium from the brine and yield aLiCl solution. Dissolution and degradation of the active material inacid is limited due to the coating providing a protective barrier.Dissolution of the active material is measured by through elementalanalysis of the acid solution following stirring.

Example 2 Lithium Extraction Using an Ion Exchange Column Loaded withBeads Comprising Coated Ion Exchange Particles

Lithium is extracted from a brine using an ion exchange column loadedwith beads containing coated ion exchange particles. The brine isnatural brine containing approximately 500 ppm Li, 50,000 ppm Na, andother chemical species including K, Mg, Ca, and sulfate. The beads arecomprised of 10 wt. % polyvinylidene fluoride (PVDF) matrix and 90 wt. %coated ion exchange particles. The coated ion exchange particles arecomprised of an active material and a protective surface coating. Theactive material is Li₄Mn₅O₁₂ and the coating is ZrO₂. The particles arecomprised of 98 wt. % active material constitutes and 2 wt. % of thecoating. The particles have a mean diameter of 1.0 microns, and thecoating thickness is approximately 2 nm.

The particles are created by first synthesizing Li₄Mn₅O₁₂ and thendepositing the coating on the surface of the Li₄Mn₅O₁₂. The beads arecreated by dissolving PVDF in N-methyl-2-pyrrolidone (NMP) to form asolution. This solution is then mixed with the coated ion exchangeparticles to form a slurry. The slurry is dripped into deionized waterto form beads. The beads have an average diameter of 2 mm and a porosityof 35%.

The ion exchange column is 2 meters in length and 50 cm in diameter. Thecolumn is loaded with the beads. 10 M HCl is pumped into the bottom ofthe column to elute a LiCl solution out the top of the column. Theparticles absorb hydrogen while releasing lithium to yield LiCl. TheLi₄Mn₅O₁₂ active material is converted to a hydrated state with ahydrogen-rich composition Li_(4-x)H_(x)Mn₅O₁₂. Lithium recovery from thecolumn is monitored using pH measurements and elemental analysis. Afterlithium recovery, the column is flushed with water.

After acid treatment, brine is pumped down through the column. Theparticles absorb lithium while releasing hydrogen. The hydrated materialis converted to a lithiated state with a lithium-rich compositionLi_(4-x)H_(x)Mn₅O₁₂. Lithium uptake by the ion exchange beads in thecolumn is monitored using pH measurements and elemental analysis. Thebrine exiting the column is adjusted to a neutral pH using NaOH and thenreinjected into a brine reservoir. After lithium uptake, the column isflushed with water.

The column is operated by repeating the previously described steps ofacid and brine pumping in alternation. This column operation functionsto extract lithium from the brine and produce a concentrated LiClsolution. During column operation, the ion exchange particles areprotected from dissolution and degradation due to the surface coating,which provides a protective barrier.

The LiCl solution that is yielded from column operation is processedinto lithium raw materials including Li₂CO₃, LiOH, and Li metal. Theselithium raw materials are sold for use in batteries, alloys, and otherproducts.

Example 3 Lithium Extraction Using Recirculating Batch System withMixing Tank, Settling Tank, and Recirculation Tanks

Lithium is extracted from a brine using a recirculating batch system(FIG. 1) comprising an ion exchange column (101), a mixing tank for base(102), a settling tank for basic precipitates (103), a brinerecirculation tank (104), and an acid recirculation tank (105). Thebrine is a natural aqueous chloride solution containing approximately100 ppm Li, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg. The ionexchange column is loaded with a packed bed of porous ion exchange beads(FIG. 8). The porous ion exchange beads are comprised of ion exchangeparticles and a polymer matrix. The ion exchange particles are coatedion exchange particles comprised of a Li₄Mn₅O₁₂ core with a ZrO₂ coating(FIG. 7). The particles are approximately spherical with a mean diameterof 3.0 microns, and the coating thickness is approximately 4.0 nm. Thepolymer matrix is comprised of polyvinylidene difluoride. The porousbeads contain porous networks with a controlled distribution of poresizes providing diffusion channels from the bead surface into the beadinterior and to the ion exchange particles. The beads have adistribution of shapes with a 2.0 mm average diameter.

The ion exchange column is 50 cm tall and 1.3 cm in diameter. 200 mL of1.0 M HCl acid is loaded into the acid recirculation tank. The acid ispumped through the ion exchange column at a flow rate of 10 mL perminute. The acid solution flows through the ion exchange column, wherethe protons from the acid enter the ion exchange beads and are exchangedfor lithium. Lithium is thereby released from the beads and enters theacid solution. The acid solution flows back into the acid recirculationtank and is recirculated through the column for a period of 6 hours.After this 6-hour time period, the acid solution has been converted to alithium chloride solution with some HCl remaining. The lithium chloridesolution with some HCl remaining is removed from the system and furtherprocessed to produce lithium carbonate powder.

500 mL of water is loaded into the acid recirculation tank. The water ispumped through the ion exchange column at a flow rate of 20 mL perminute to wash residual acid from the column. The water flows throughthe ion exchange column, then back into the acid recirculation tank, andis then recirculated through the ion exchange column. After 2 hours ofwater washing, the water is removed from the acid recirculation tank,the pH of the water is neutralized, and the water is discarded.

10 liters of brine is loaded into the brine recirculation tank. Thebrine is pumped through the ion exchange column at a flow rate of 40 mLper minute. As the brine flows through the column, the ion exchangebeads absorb lithium from the brine while releasing protons. Theacidified brine flows out of the ion exchange column and into a mixingtank, where aqueous NaOH base is injected from an aqueous base tank(106) to adjust the pH of the brine to approximately 7.5. The mixingtank mixes the base into the brine. The brine flows from the mixing tankinto the settling tank, where Mg(OH)₂ precipitates optionally settle tothe bottom. The Mg(OH)₂ precipitates, which form an aqueous slurry, arepumped from the bottom of the settling tank and reinjected into themixing tank. The pH of the brine entering and leaving the mixing tank ismonitored to control rates of base injection into the mixing tank. Thebrine leaves the settling tank and enters into the brine recirculationtank. The brine is then recirculated back into the ion exchange column.After 36 hours, the rate of lithium uptake by the ion exchange beadsslows, pumping through the system is terminated, and the spent brine isdrained from the system and discarded. Then, the system is again washedwith 500 mL of water as described previously. Then, the system is elutedwith acid as described previously to recover a lithium concentrate.

These system operations are repeated to extract lithium from brine andyield a lithium chloride concentrate for production of lithium carbonateor other lithium chemicals.

Example 4 Lithium Extraction Using Recirculating Batch System withMixing Tank and Recirculation Tanks

Lithium is extracted from a brine using a recirculating batch system(FIG. 2) comprising an ion exchange column (201), a mixing tank for base(202), a brine recirculation tank (203), and an acid recirculation tank(204). The brine is a natural aqueous chloride solution containingapproximately 100 ppm Li, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppmMg. The ion exchange column is loaded with a packed bed of porous ionexchange beads. The porous ion exchange beads are comprised of ionexchange particles and a polymer matrix. The ion exchange particles arecoated ion exchange particles comprised of a Li₄Mn₅O₁₂ core with a ZrO₂coating. The particles are approximately spherical with a mean diameterof 3.0 microns, and the coating thickness is approximately 4.0 nm. Thepolymer matrix is comprised of polyvinylidene fluoride. The porous beadscontain porous networks with a controlled distribution of pore sizesproviding diffusion channels from the bead surface into the beadinterior and to the ion exchange particles. The beads have adistribution of shapes with a 2.0 mm average diameter.

The ion exchange column is 50 cm tall and 1.3 cm in diameter. 200 mL of1.0 M HCl acid is loaded into the acid recirculation tank. The acid ispumped through the ion exchange column at a flow rate of 10 mL perminute. The acid solution flows through the ion exchange column, wherethe protons from the acid enter the ion exchange beads and are exchangedfor lithium. Lithium is thereby released from the beads and enters theacid solution. The acid solution is flowed back into the acidrecirculation tank and is recirculated through the column for a periodof 6 hours. After this 6-hour time period, the acid solution has beenconverted to a lithium chloride solution with some HCl remaining. Thelithium chloride solution with some HCl remaining is removed from thesystem and further processed to produce lithium carbonate powder.

500 mL of water is loaded into the acid recirculation tank. The water ispumped through the ion exchange column at a flow rate of 20 mL perminute to water residual acid from the column. The water flows throughthe ion exchange column, then back into the acid recirculation tank, andis then recirculated through the ion exchange column. After 2 hours ofwater washing, the water is removed from the acid recirculation tank,the pH of the water is neutralized, and the water is discarded.

10 liters of brine is loaded into the brine recirculation tank. Thewater is pumped through the ion exchange column at a flow rate of 40 mLper minute. As the brine flows through the column, the ion exchangebeads absorb lithium from the brine while releasing protons. Theacidified brine flows out of the ion exchange column and into a mixingtank, where aqueous NaOH base is injected from an aqueous base tank(205) to adjust the pH of the brine to approximately 7.0 while limitingformation of any basic precipitates. The mixing tank mixes the base intothe brine. The pH of the brine entering and leaving the mixing tank ismonitored to control rates of base injection into the mixing tank. Thebrine leaves the mixing tank and enters into the brine recirculationtank. The brine is then recirculated back into the ion exchange column.After 36 hours, the rate of lithium uptake by the ion exchange beadsslows, pumping through the system is terminated, and the spent brine isdrained from the system and discarded. Then, the system is again washedwith 500 mL of water as described previously. Then, the system is elutedwith acid as described previously to recover a lithium concentrate.

These system operations are repeated to extract lithium from brine andyield a lithium chloride concentrate for production of lithium carbonateor other lithium chemicals.

Example 5 Lithium Extraction Using Column Interchange System with BrineCircuit, Acid Circuit, and Water Washing Circuit

Lithium is extracted from a brine using a column interchange system(FIG. 3) comprising six ion exchange columns, which are divided into abrine circuit, a water washing circuit, and an acid circuit. The brineis a natural aqueous chloride solution containing approximately 50 ppmLi, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg. The ion exchangecolumns are loaded with packed beds of porous ion exchange beads. Theporous ion exchange beads are comprised of ion exchange particles and apolymer matrix. The ion exchange particles are coated ion exchangeparticles comprised of a Li₄Mn₅O₁₂ core with a ZrO₂ coating. Theparticles are approximately spherical with a mean diameter of 3.0microns, and the coating thickness is approximately 4.0 nm. The polymermatrix is comprised of polyvinylidene fluoride. The porous beads containporous networks with a controlled distribution of pore sizes providingdiffusion channels from the bead surface into the bead interior and tothe ion exchange particles. The beads have a distribution of shapes witha 2.0 mm average diameter.

Each of the six ion exchange columns is 150 cm tall and 75 cm indiameter (303, 305, 307, 311, 314, 316). Each ion exchange column has anassociated mixing tank for mixing base into brine before the brine isinjected into the column (302, 304, 306, 310, 313, 315). Three of thecolumns (303, 305, 307) along with the associated mixing tanks (302,304, 306) are linked to form a brine circuit. Brine flows from a brinepipe (301) through a first mixing tank (302), a first ion exchangecolumn (303), a second mixing tank (304), a second ion exchange column(305), a third mixing tank (306), a third ion exchange column (307), andthen into a disposal pipe (308). For the mixing tanks in the brinecircuit (303, 305, 307), an aqueous base solution of NaOH is added toincrease the pH of the brine to 7.5. The pH of the brine is monitoredbefore and after each mixing tank in the brine circuit to control therate of addition of aqueous base solution. In the first mixing tank(302) in the brine circuit, the brine enters the mixing tank from thebrine pipe at a pH of 6.5 and a relatively small amount of base isadded. In the other mixing tanks in the brine circuit (304, 306), thebrine enters the mixing tank from the outlet of prior ion exchangecolumns at a pH of 3.5, and a relatively larger amount of base is addedto neutralize the protons that are released by the prior ion exchangecolumns.

The water washing circuit involves pumping water from a water pipe(309), through an ion exchange column that is saturated with lithium(311), and then the water is pumped into a disposal pipe. This waterwashing circuit removes residual brine from the column to prepare foracid elution with minimal impurities.

The acid circuit comprises two ion exchange columns, which are elutedwith 1.0 M sulfuric acid to yield a lithium sulfate concentrate. Acidsolution flows from an acid storage tank (312), into a first ionexchange column in the acid circuit (314) and then into a second ionexchange column in the acid circuit (316). The mixing tanks associatedwith the acid circuit are idle (313, 315). While the acid flows throughthe acid circuit, the ion exchange beads absorb protons while releasinglithium to form a lithium sulfate solution. The resulting lithiumsulfate concentrate flows into a lithium concentrate pipe (317), and isthen moved to a conversion plant for processing into battery-gradelithium hydroxide.

The flow rates of the brine circuit, water washing circuit, and acidcircuit are coordinated for an interchange event, which is marked by theswitching of values to redirect flows through the system. During theinterchange event, the first column in the brine circuit is interchangedto the water washing circuit, the column in the water washing circuit isinterchanged to the acid circuit, and the first column in the acidcircuit is interchanged to the brine circuit.

As the brine flows through the brine circuit, lithium is absorbed intothe ion exchange beads in the ion exchange columns. The first ionexchange column in the brine circuit becomes saturated with lithiumfirst, and then this first column is interchanged to the water washingcircuit. As acid solution flows through the acid circuit, lithium isreleased from the ion exchange beads in the ion exchange columns. Thefirst ion exchange column in the acid circuit becomes saturated withprotons first, and then this first column is interchanged to the end ofthe brine circuit. Residual acid in the ion exchange column at the endof the brine circuit is washed out by the brine and is pH neutralizedprior to disposal.

After the interchange event, the brine circuit is comprised of three ionexchange columns (320, 322, 324) and three mixing tanks for baseaddition (319, 321, 323). The acid circuit is comprised of two ionexchange columns (331, 333). The mixing tanks associated with the acidcircuit are idle (330, 332). The water washing circuit is comprised ofone ion exchange column (328). After the interchange event, the brinepipe (318), water pipe (326), acid tank (329), disposal pipe (325), andlithium concentrate pipe (324) are interchanged to the new circuitsusing valves.

In alternative versions of this example, the brine circuit is optionallycomprised of fifty or more ion exchange columns with associated basemixing tanks for each column. This large number of ion exchange columnsand mixing tanks enables high lithium recoveries from brines withconcentrations of lithium above 50 ppm, while maintaining the pH of thebrine in the range of 4-8. Such a large number of ion exchange columnsis difficult to illustrate, and so a brine circuit with only threecolumns is used in this example to facilitate the description andillustration.

Example 6 Lithium Extraction Using Column Interchange System with BrineCircuit, Acid Recirculating Loop, and Water Washing Circuit

Lithium is extracted from a brine using a column interchange system(FIG. 4) comprising five ion exchange columns, which are divided into abrine circuit, a water washing circuit, and an acid recirculating loop.The brine is a natural aqueous chloride solution containingapproximately 50 ppm Li, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg.The ion exchange columns are loaded with packed beds of porous ionexchange beads. The porous ion exchange beads are comprised of ionexchange particles and a polymer matrix. The ion exchange particles arecoated ion exchange particles comprised of a Li₄Mn₅O₁₂ core with a ZrO₂coating. The particles are approximately spherical with a mean diameterof 3.0 microns, and the coating thickness is approximately 4.0 nm. Thepolymer matrix is comprised of polyvinylidene fluoride. The porous beadscontain porous networks with a controlled distribution of pore sizesproviding diffusion channels from the bead surface into the beadinterior and to the ion exchange particles. The beads have adistribution of shapes with a 2.0 mm average diameter.

Each of the five ion exchange columns is 150 cm tall and 75 cm indiameter (403, 405, 407, 411, 414). Each ion exchange column has anassociated mixing tank for mixing base into brine before the brine isinjected into the column (402, 404, 406, 410, 413). Three of the columns(403, 405, 407) along with the associated mixing tanks (402, 404, 406)are linked to form a brine circuit. Brine flows from a brine pipe (401)through a first mixing tank (402), a first ion exchange column (403), asecond mixing tank (404), a second ion exchange column (405), a thirdmixing tank (406), a third ion exchange column (407), and then into adisposal pipe (408). For the mixing tanks in the brine circuit (403,405, 407), an aqueous base solution of NaOH is added to increase the pHof the brine to 7.5. The pH of the brine is monitored before and aftereach mixing tank in the brine circuit to control the rate of addition ofaqueous base solution. In the first mixing tank (402) in the brinecircuit, the brine enters the mixing tank from the brine pipe at a pH of6.5 and a relatively small amount of base is added. In the other mixingtanks in the brine circuit (404, 406), the brine enters the mixing tankfrom the outlet of prior ion exchange columns at a pH of 3.5, and arelatively larger amount of base is added to neutralize the protons thatare released by the prior ion exchange columns.

The water washing circuit involves pumping water from a water pipe(409), through an ion exchange column that is saturated with lithium(411), and then the water is pumped into a disposal pipe. This waterwashing circuit removes residual brine from the column to prepare foracid elution with minimal impurities.

The acid recirculating loops comprises one ion exchange column (414) andan acid recirculation tank (412). The tank is loaded with 1.0 M HClacid, which is pumped into the ion exchange column, then back into thetank, then recirculated through the column. As the acid solution flowsthrough the column, the ion exchange beads absorb protons whilereleasing lithium. Over time, the acid solution is converted into alithium chloride concentrate. The mixing tanks associated with the ionexchange column are idle (413). The resulting lithium chlorideconcentrate is then pH neutralized, concentrated through reverseosmosis, polished to remove trace amounts of divalent ions, andprocessed through carbonation to yield a battery-grade lithium carbonatepowder.

The flow rates of the brine circuit, water washing circuit, and acidrecirculation loop are coordinated for an interchange event, which ismarked by the switching of values to redirect flows through the system.During the interchange event, the first column in the brine circuit isinterchanged to the water washing circuit, the column in the waterwashing circuit is interchanged to the acid recirculation loop, and thecolumn in the acid circulation loop is interchanged to the brinecircuit.

As the brine flows through the brine circuit, lithium is absorbed intothe ion exchange beads in the ion exchange columns. The first ionexchange column in the brine circuit becomes saturated with lithiumfirst, and then this first column is interchanged to the water washingcircuit. The ion exchange column in the acid recirculation loop becomessaturated with protons, and then this column is interchanged to the endof the brine circuit. Residual acid in the ion exchange column at theend of the brine circuit is washed out by the brine and is pHneutralized prior to disposal.

After the interchange event, the brine pipe (401), water pipe (409),acid tank (412), and disposal pipe (408) are interchanged to the newcircuits using valves.

In alternative versions of this example, the brine circuit is optionallycomprised of fifty or more ion exchange columns with associated basemixing tanks for each column. This large number of ion exchange columnsand mixing tanks enables high lithium recoveries from brines withconcentrations of lithium above 50 ppm, while maintaining the pH of thebrine in the range of 4-8. Such a large number of ion exchange columnsis difficult to illustrate, and so a brine circuit with only threecolumns is used in this example to facilitate the description andillustration.

Example 7 Lithium Extraction Using Stirred Tank System

Lithium is extracted from a brine using a stirred tank system (FIG. 5)comprising a tank (501), a mixing tank for addition of base (502), abrine recirculation pipe (503), a permeable compartment for supportingion exchange beads inside the tank (504), and an acid recirculation pipe(505). The brine is a natural aqueous chloride solution containingapproximately 100 ppm Li, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppmMg. The ion exchange column is loaded with a packed bed of porous ionexchange beads. The porous ion exchange beads are comprised of ionexchange particles and a polymer matrix. The ion exchange particles arecoated ion exchange particles comprised of a Li₄Mn₅O₁₂ core with a ZrO₂coating. The particles are approximately spherical with a mean diameterof 3.0 microns, and the coating thickness is approximately 4.0 nm. Thepolymer matrix is comprised of polyvinylidene fluoride. The porous beadscontain porous networks with a controlled distribution of pore sizesproviding diffusion channels from the bead surface into the beadinterior and to the ion exchange particles. The beads have adistribution of shapes with a 2.0 mm average diameter.

The tank is 3.5 meters tall and 2.5 meters in diameter (501). Thepermeable compartment for supporting ion exchange beads is mountedinside the tank near the bottom of the tank. The compartment is mountedlow enough in the tank so that the compartment will be submerged by theminimum volume of acid needed to elute the lithium from the beads. Thecompartment containing beads is loaded into the tank with the beads in alithiated state. 1.0 M HCl acid is then loaded into the tank andrecirculated through the acid circulation pipe (505). This acid solutiondelivers protons to the beads while absorbing lithium from the beads.The acid solution is pumped out of the tank at a point above thecompartment, through the acid circulation pipe, and is then reinjectedinto the bottom of the tank. The acid solution then percolates throughthe compartment where it contacts the ion exchange beads, elutinglithium from the beads. Once lithium elution has slowed, the resultinglithium concentrate is removed from the system and processed into abattery-grade lithium carbonate product by neutralization, concentrationusing reverse osmosis, carbonation, and recrystallization.

Water is loaded into the tank and recirculated through the acidcirculation pipe to wash out residual acid.

Brine is loaded into the tank and pumped out of the top of the tank,into the base mixing tank (502). The brine then flows through the brinecirculation pipe and is reinjected into the bottom of the tank below thecompartment. The brine flows upward through the tank, percolatingthrough the compartment. The brine contacts the ion exchange beads, andthe beads absorb lithium out of the brine while release protons. Theacidified brine flows upward above the compartment, and is then pumpedinto the base mixing tank. In the base mixing tank, an aqueous base NaOHsolution is added to neutralize the protons released by the beads andmaintain the pH of the brine in the range of 6-8. The neutralized brinethen flows through the brine recirculation pipe and is recirculated backinto the tank for additional lithium uptake. After lithium uptake slows,the spent brine is removed from the tank. The tank is then washed againwith water as described previously. Then, the acid step is repeated toyield a lithium chloride concentrate. This cycle is repeated to yieldlithium concentrate, which is processed into battery-grade lithiumcarbonate.

Example 8 Lithium Extraction Using Ported Ion Exchange Column System

Lithium is extracted from a brine using a ported ion exchange columnsystem (FIG. 6) comprising a column (602) with multiple base injectionports (604). The brine is a natural aqueous chloride solution containingapproximately 100 ppm Li, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppmMg. The ion exchange column is loaded with a packed bed of porous ionexchange beads. The porous ion exchange beads are comprised of ionexchange particles and a polymer matrix. The ion exchange particles arecoated ion exchange particles comprised of a Li₄Mn₅O₁₂ core with a ZrO₂coating. The particles are approximately spherical with a mean diameterof 3.0 microns, and the coating thickness is approximately 4.0 nm. Thepolymer matrix is comprised of polyvinylidene fluoride. The porous beadscontain porous networks with a controlled distribution of pore sizesproviding diffusion channels from the bead surface into the beadinterior and to the ion exchange particles. The beads have adistribution of shapes with a 2.0 mm average diameter.

Ion exchange beads are loaded into the ported ion exchange columnsystem. 1.0 M HCl acid is flowed through the system to elute a lithiumchloride concentrate. Then, the system is washed with acid to removeresidual acid. Brine is flowed into the bottom of the system from abrine pipe (601). As the brine flows through the column, the beadsabsorb lithium out of the brine and release protons into the brine,acidifying the brine. To maintain the pH of the brine in a pH range of4-8, an aqueous base solution of NaOH is injected into the baseinjection ports. As brine first enters the column and contacts freshbeads near the bottom of the column, the ion exchange reaction isfastest near the bottom of the column, and so initially base is injectedthrough the ports at the bottom of the column at a higher rate. As thebeads near the bottom of the column saturate, the region of the columnwith the greatest rate of ion exchange moves upward in the column. Toneutralize the protons being release in the brine higher up in thecolumn, base is then injected higher up in the column and base injectionnear the bottom of the column is slowed and eventually terminated. Baseinjection at the bottom of the column is terminated to avoid theprecipitation of Mg(OH)₂ and other basic precipitates in the column inregions where protons are no longer being released at sufficient ratesto neutralize the base. As the brine moves upward through the column, pHis maintained in a range of 4-8 while the beads absorb lithium andrelease protons and while formation of basic precipitations is limited.Once the beads throughout the column are saturated or nearly saturatedwith lithium, the column is washed with water, and the lithium is elutedwith sulfuric acid to form a lithium sulfate concentrate. The lithiumconcentrate is then processed into a lithium hydroxide product.

Example 9 Lithium Extraction with Two Types of Moving Bed Columns

Lithium is extracted from a brine using an ion exchange column loadedwith a moving bed of porous ion exchange particles. The brine is anatural chloride solution containing approximately 100 ppm Li, 40,000ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg. The porous ion exchange beadsare comprised of ion exchange particles and a polymer matrix. The ionexchange particles are comprised of a Li4Mn5O12 core with a ZrO₂coating. The ion exchange particles contain 99 wt. % Li₄Mn₅O₁₂ and 1 wt.% ZrO₂. The particles are approximately spherical with a mean diameterof 1.0 microns, and the coating thickness is approximately 1.0 nm. Thepolymer matrix is comprised of PVC. The porous beads contain pores witha distribution of pore sizes providing diffusion channels from the beadsurface into the bead interior and to the ion exchange particles. Whenthe porous beads are submerged in aqueous or other solutions, the poresare infiltrated with the solutions. The beads have a distribution ofshapes that are approximately spherical on average with a 1.0 mm averagediameter.

The porous ion exchange beads are created by combining three components:ion exchange particles, a polymer, and a removable filler material. Thefiller material is potassium sulfate. The three components are mixedtogether using a solvent mixture of n-methyl-2-pyrrolidone, ethanol, andwater, and then the solvent is removed. The resulting mixture is groundand formed into beads using a mechanical press. The beads are heated toalter the structure of the polymer and improve mechanical strength. Thefiller is removed using water, which dissolves the filler and therebyleaves behind pores throughout the bead. The bead is heated again toalter the structure of the polymer and further improve mechanicalstrength.

Lithium is extracted from the brine in a continuous process with porousbeads moving between two types of ion exchange columns. One type of ionexchange column is an acid column, where acid is pumped through thecolumn. The other type of ion exchange column is a brine column, wherebrine is pumped through the column.

The acid columns are 2.0 meters in length and 1.0 meters in diameter.Each column is loaded with a moving bed of porous beads. 1.0 M HCl acidis pumped through the column from the bottom to the top at a flow rateof 0.5 bed volumes per hour to elute a LiCl solution. The pores in thebeads allow the acid solution to penetrate into the bead and access theion exchange particles. Therefore, the ion exchange particles can absorbhydrogen from the acid while releasing lithium into the acid. TheLi₄Mn₅O₁₂ active material is converted to a hydrogenated state with ahydrogen-rich composition Li_(4-x)H_(x)Mn₅O₁₂ where x may be close to 2.The ZrO₂ coating allows diffusion of hydrogen and lithium respectivelyto and from the active material while providing a protective barrierthat limits dissolution of manganese and oxygen from the activematerial. The beads release lithium to yield a LiCl solution with alithium concentration of approximately 0.8 M in solution. Lithiumrecovery from the column is monitored using pH measurements andelemental analysis. The beads are loaded into the top of the column andare moved toward the bottom of the column by a corkscrew mechanism. Atthe bottom of the column, the beads are removed from the column usinganother corkscrew mechanism. The beads are then washed with water andtransferred to a brine column.

The brine columns are 3.0 meters in length and 1.0 meters in diameter.Each column is loaded with a moving bed of porous beads. Brine is pumpedthrough the column from the bottom to the top at a flow rate of 4.0 bedvolumes per hour. The beads absorb lithium while releasing hydrogen. Thepores in the beads allow the brine solution to penetrate into the beadand access the ion exchange particles. Therefore, the ion exchangeparticles can absorb lithium from the brine while releasing hydrogeninto the brine. The beads are converted from a hydrogenated state to alithiated state with a lithium-rich composition Li₄Mn₅O₁₂ where x may beclose to 0. Lithium uptake by the beads in the column is monitored usingpH measurements and elemental analysis. The brine exiting the column isadjusted to a neutral pH using NaOH and then reinjected into a brinereservoir. The beads are loaded into the top of the column and are movedtoward the bottom of the column by a corkscrew mechanism. At the bottomof the column, the beads are removed from the column using anothercorkscrew mechanism. The beads are then washed with water andtransferred back to an acid column.

The acid and brine columns are operated in a continuous process bycontinuously flowing acid and brine through the respective columns. Thebeads move continuously through the columns. In the brine column, eachbead is removed from the column as lithium uptake into the bead beginsto slow due to partial saturation. In the acid column, each bead isremoved from the column as lithium release from the bead begins to slowdue to partial saturation. Removal of the bead from the acid columnminimizes the time that the bead spends in acid while ensuring adequatelithium extraction from the bead. This protects the lifespan of thebead. These column operations function to extract lithium from the brineand produce a concentrated LiCl solution. During column operations, theporous beads allow the acid and brine solutions to penetrate into thebeads and deliver hydrogen and lithium to the ion exchange particles.The ion exchange particles are protected from dissolution anddegradation due to the ZrO₂ surface coating, which provides a protectivebarrier.

The LiCl solution that is yielded from the column operations isprocessed into lithium raw materials including Li₂CO₃, LiOH, LiCL, andLi metal. These lithium raw materials are sold for use in batteries,alloys, and other products.

Example 10 Lithium Extraction with Four Types of Moving Bed Columns

Lithium is extracted from a brine using an ion exchange column loadedwith a moving bed of porous ion exchange particles. The brine is anatural chloride solution containing approximately 100 ppm Li, 40,000ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg. The porous ion exchange beadsare comprised of ion exchange particles and a polymer matrix. The ionexchange particles are comprised of a Li₄Mn₅O₁₂ core with a ZrO₂coating. The ion exchange particles contain 99 wt. % Li₄Mn₅O₁₂ and 1 wt.% ZrO₂. The particles are approximately spherical with a mean diameterof 1.0 microns, and the coating thickness is approximately 1.0 nm. Thepolymer matrix is comprised of PVC. The porous beads contain pores witha distribution of pore sizes providing diffusion channels from the beadsurface into the bead interior and to the ion exchange particles. Whenthe porous beads are submerged in aqueous or other solutions, the poresare infiltrated with the solutions. The beads have a distribution ofshapes that are approximately spherical on average with a 1.0 mm averagediameter.

The porous ion exchange beads are created by combining three components:ion exchange particles, a polymer, and a removable filler material. Thefiller material is potassium sulfate. The three components are mixedtogether using a solvent mixture of n-methyl-2-pyrrolidone, ethanol, andwater, and then the solvent is removed. The resulting mixture is groundand formed into beads using a mechanical press. The beads are heated toalter the structure of the polymer and improve mechanical strength. Thefiller is removed using water, which dissolves the filler and therebyleaves behind pores throughout the bead. The bead is heated again toalter the structure of the polymer and further improve mechanicalstrength.

Lithium is extracted from the brine in a continuous process with porousbeads moving between four types of columns. The first type of column isan acid ion exchange column, where acid is pumped through the column todeliver hydrogen to the beads and release lithium. The second type ofcolumn is a water column, where residual acid is washed from the beads.The third type of column is a brine ion exchange column, where brine ispumped through the column to deliver lithium to the beads whilereleasing hydrogen. The fourth type of column is a water column, whereresidual brine is washed from the beads.

The acid columns are 2.0 meters in length and 1.0 meters in diameter.Each column is loaded with a moving bed of porous beads. 1.0 M HCl acidis pumped through the column from the bottom to the top at a flow rateof 0.5 bed volumes per hour to elute a LiCl solution. The pores in thebeads allow the acid solution to penetrate into the bead and access theion exchange particles. Therefore, the ion exchange particles can absorbhydrogen from the acid while releasing lithium into the acid. TheLi₄Mn₅O₁₂ active material is converted to a hydrogenated state with ahydrogen-rich composition Li_(4-x)H_(x)Mn₅O₁₂ where x may be close to 2.The ZrO₂ coating allows diffusion of hydrogen and lithium respectivelyto and from the active material while providing a protective barrierthat limits dissolution of manganese and oxygen from the activematerial. The beads release lithium to yield a LiCl solution with alithium concentration of approximately 0.8 M in solution. Lithiumrecovery from the column is monitored using pH measurements andelemental analysis. The beads are loaded into the top of the column andare moved toward the bottom of the column by a corkscrew mechanism. Atthe bottom of the column, the beads are removed from the column usinganother corkscrew mechanism.

The beads are then transferred to another column with a moving bed ofbeads, where the beads are washed with water to remove residual acid.The water flows in opposite direction of the bead movement. The beadsare then transferred to a brine column.

The brine columns are 3.0 meters in length and 1.0 meters in diameter.Each column is loaded with a moving bed of porous beads. Brine is pumpedthrough the column from the bottom to the top at a flow rate of 4.0 bedvolumes per hour. The beads absorb lithium while releasing hydrogen. Thepores in the beads allow the brine solution to penetrate into the beadand access the ion exchange particles. Therefore, the ion exchangeparticles can absorb lithium from the brine while releasing hydrogeninto the brine. The beads are converted from a hydrogenated state to alithiated state with a lithium-rich composition Li₄Mn₅O₁₂ where x may beclose to 0. Lithium uptake by the beads in the column is monitored usingpH measurements and elemental analysis. The brine exiting the column isadjusted to a neutral pH using NaOH and then reinjected into a brinereservoir. The beads are loaded into the top of the column and are movedtoward the bottom of the column by a corkscrew mechanism. At the bottomof the column, the beads are removed from the column using anothercorkscrew mechanism.

The beads are then transferred to another column with a moving bed ofbeads, where the beads are washed with water to remove residual brine.The water flows in opposite direction of the bead movement. The beadsare then transferred back to an acid column.

The acid and brine columns are operated in a continuous process bycontinuously flowing acid and brine through the respective columns. Thebeads move continuously through the columns. In the brine column, eachbead is removed from the column as lithium uptake into the bead beginsto slow due to partial saturation. In the acid column, each bead isremoved from the column as lithium release from the bead begins to slowdue to partial saturation. Removal of the bead from the acid columnminimizes the time that the bead spends in acid while ensuring adequatelithium extraction from the bead. This protects the lifespan of thebead. These column operations function to extract lithium from the brineand produce a concentrated LiCl solution. During column operations, theporous beads allow the acid and brine solutions to penetrate into thebeads and deliver hydrogen and lithium to the ion exchange particles.The ion exchange particles are protected from dissolution anddegradation due to the ZrO₂ surface coating, which provides a protectivebarrier.

The LiCl solution that is yielded from the column operations isprocessed into lithium raw materials including Li₂CO₃, LiOH, LiCL, andLi metal. These lithium raw materials are sold for use in batteries,alloys, and other products.

Example 11 Lithium Extraction Using Stirred Tank Reactor

Lithium was extracted from a brine using a stirred tank reactor loadedwith a fluidized bed of ion exchange particles. The brine was a naturalchloride solution containing 500 ppm Li, 60,000 ppm Na, 17,000 ppm Ca,and 3,000 ppm Mg. The ion exchange particles were comprised of aLi₄Mn₅O₁₂ core with a titanium dioxide coating. The ion exchangeparticles contained 98 wt. % Li₄Mn₅O₁₂ and 2 wt. % titanium dioxide. Theparticles were approximately spherical with a mean diameter of 50microns.

The ion exchange particles were loaded into a stirred tank reactor (FIG.16) comprising a tank (2101), an overhead stirrer (2102), a pH probe(2103), and a pipe for adding base into the tank (2104). The particleswere sequentially stirred with brine, water, 0.75 N sulfuric acid, andagain with water. When the particles were stirred with brine, theparticles absorbed lithium from the brine while releasing protons intothe brine. As protons were released, the pH of the brine dropped. The pHprobe measured the change in pH and triggered base to be added to thebrine through the pipe. This base neutralized the protons released fromthe particles and maintained a strong thermodynamic driving force forlithium uptake into the particles. The particles were then washed withwater to remove residual brine. Then, the particles were eluted withsulfuric acid, and the particles released lithium to form a lithiumsulfate solution while absorbing protons. Then, the particles werewashed again to remove residual acid. Then, the particles were returnedto a brine step and the cycle repeated. This cycle functioned to extractlithium from the brine and produce a lithium sulfate solution.

Example 12 Lithium Extraction Using Stirred Tank Reactor withCompartment

Lithium was extracted from a brine using a stirred tank reactor loadedwith a fluidized bed of ion exchange particles. The brine was a naturalchloride solution containing 500 ppm Li, 60,000 ppm Na, 17,000 ppm Ca,and 3,000 ppm Mg. The ion exchange particles were comprised of Li₄Mn₅O₁₂in a polystyrene matrix. The particles contained approximately 90%Li₄Mn₅O₁₂ and 10% polystyrene. The particles had a typical size of 100microns.

The ion exchange particles were loaded into a stirred tank reactor (FIG.17) comprising a tank (2201), an overhead stirrer (2202), a pH probe(2203), a pipe for adding base into the tank (2204), and a compartmentthat contains the ion exchange particles with a porous polymer support(2205). The porous polymer support was a polyether ether ketone meshwith 35 micron pore size. The porous polymer support divided the bottomof the tank from the top of the tank, contained the ion exchangeparticles in the top of the tank, and allowed fluid to drain out of thetank through the mesh and into a pipe connected at the bottom of thetank. The compartment represented approximately 99% of the volume of thetank.

The particles were sequentially stirred with brine, water, 0.75 Nhydrochloric acid, and again with water. When the particles were stirredwith brine, the particles absorbed lithium from the brine whilereleasing protons into the brine. As protons were released, the pH ofthe brine dropped. The pH probe measured the change in pH and triggeredbase to be added to the brine through the pipe. This base neutralizedthe protons released from the particles and maintained a strongthermodynamic driving force for lithium uptake into the particles. Thebrine was drained from the tank through the bottom while leaving the ionexchange particles in the compartment separated by the porous mesh. Theparticles were then washed with water three times to remove residualbrine, and each time the water was drained from the bottom of the tank.Then, the particles were eluted with hydrochloric acid, and theparticles released lithium to form a lithium chloride solution whileabsorbing protons. Then, the lithium chloride solution was drained fromthe bottom of the tank. Then, the particles were washed again to removeresidual acid. Then, the particles were returned to a brine step and thecycle repeated. This cycle functioned to extract lithium from the brineand produce a lithium chloride solution. The lithium chloride wasconcentrated through evaporation, purified, and reacted with sodiumcarbonate to form a lithium carbonate powder.

Example 13 Lithium Extraction Using Pair of Stirred Tank Reactors

Lithium is extracted from a brine using a stirred tank reactor loadedwith a fluidized bed of ion exchange particles. The brine is a naturalchloride solution containing approximately 500 ppm Li, 60,000 ppm Na,20,000 ppm Ca, and 5,000 ppm Mg. The ion exchange particles arecomprised of a Li₄Mn₅O₁₂ material. The particles are approximatelyspherical with a mean diameter of 30 microns.

The ion exchange particles are loaded into an ion exchange system (FIG.18) comprising a large stirred tank reactor and a small stirred tankreactor. The large stirred tank reactor comprises a large tank (2301),an overhead stirrer (2302), a pH probe (2303), a pipe for adding baseinto the tank (2304), and a compartment that contains the ion exchangeparticles with a porous polymer support (2305). The small stirred tankreactor comprises a small tank (2306), an overhead stirrer (2307), and acompartment that contains the ion exchange particles with a porouspolymer support (2308). The porous polymer supports are formed with abilayer structure with a coarse polypropylene mesh (750 micron pores)and a fine polyether ether ketone mesh (20 micron pores). The porouspolymer support divides the bottom of the tanks from the top of thetanks, contains the ion exchange particles in the top of the tanks, andallows fluid to drain out of the tanks through the mesh and into pipesconnected at the bottoms of the tanks. The compartments represent 99% ofthe volume of the tanks.

In the compartment of the large stirred tank reactor, the particles arestirred with brine and the water. When the particles are stirred withbrine, the particles absorb lithium from the brine while releasingprotons into the brine. As protons are released, the pH of the brinedrops. The pH probe measures the change in pH and triggers base to beadded to the brine through the pipe. This base neutralizes the protonsreleased from the particles and maintains a strong thermodynamic drivingforce for lithium uptake into the particles. The brine is drained fromthe tank through the mesh and out the bottom while leaving the ionexchange particles in the compartment separated by the porous mesh. Theparticles are then washed with water to remove residual brine, and thewater is drained from the bottom of the tank. Then, water is added tothe tank to form a slurry, which is pumped out of the large stirred tankreactor and into the compartment of the small stirred tank reactor.

In the small stirred tank reactor, the particles are washed again withwater and the water is then drained through the mesh out the bottom ofthe tank. Then, the particles are stirred with hydrochloric acid, andthe particles release lithium to form a lithium chloride solution whileabsorbing protons. Then, the lithium chloride solution is drained fromthe bottom of the tank. Then, the particles are washed again to removeresidual acid. Then, water is added to form a slurry, and the slurry ispumped back to the large stirred tank reactor.

The lithium chloride is concentrated through evaporation and purified.Then, the lithium chloride solution is mixed with a solution of sodiumcarbonate to precipitate lithium carbonate.

Example 14 Lithium Extraction Using Continuous Network of Stirred TankReactors

Lithium is extracted from a brine using a stirred tank reactor loadedwith a fluidized bed of ion exchange particles. The brine is a naturalchloride solution containing approximately 500 ppm Li, 60,000 ppm Na,20,000 ppm Ca, and 5,000 ppm Mg. The ion exchange particles arecomprised of a Li₄Mn₅O₁₂ material with a titanium dioxide coatingembedded into a polyvinylidene difluoride (PVDF) matrix. The ionexchange particles contain 75 wt. % Li₄Mn₅O₁₂, 5 wt. % titanium dioxide,and 20 wt. % PVDF. The particles are approximately spherical with a meandiameter of 80 microns.

The ion exchange particles are loaded into a network of stirred tankreactors, which is operated in a continuous mode (FIG. 19). The systemcomprises three large stirred tank reactors (2401, 2402, 2403) and threesmall stirred tank reactors (2404, 2405, 2406). Each large stirred tankreactor comprises a large tank, an overhead stirrer, a pH probe, a pipefor adding base into the tank, and a compartment that contains the ionexchange particles with a porous polymer support. Each of the smallstirred tank reactors comprises a small tank, an overhead stirrer, and acompartment that contains the ion exchange particles with a porouspolymer support. The porous polymer supports are formed with a bilayerstructure with a coarse polypropylene mesh (750 micron pores) and a finepolyester mesh (20 micron pores). The porous polymer support divides thebottom of the tanks from the top of the tanks, contains the ion exchangeparticles in the top of the tanks, and allows fluid to drain out of thetanks through the mesh and into pipes connected at the bottoms of thetanks. In each tank, the compartment represents about 98% of the volumeof the tank.

Brine is flowed continuously from a well field through anultra-filtration unit to remove suspended solids and into the firstlarge stirred tank reactor (2401). In the first stirred tank reactor,the brine is stirred with the ion exchange particles with a residencetime of 20 minutes and is continuously removed from the reactor from thebottom of the reactor and then pumped into the second large stirred tankreactor (2402). In the second stirred tank reactor, the brine is stirredwith the ion exchange particles with a residence time of 20 minutes andis continuously removed from the reactor from the bottom of the reactorand then pumped into the third large stirred tank reactor (2403). In thethird stirred tank reactor, the brine is stirred with the ion exchangeparticles with a residence time of 20 minutes and is continuouslyremoved from the reactor from the bottom of the reactor and thenfiltered to remove any fragments of ion exchange particles and pipedback to the well field for reinjection. When the particles are stirredwith brine, the particles absorb lithium from the brine while releasingprotons into the brine. As protons are released, the pH of the brinedrops. The pH probe measures the change in pH and triggers base to beadded to the brine through the pipe. This base neutralizes the protonsreleased from the particles and maintains a strong thermodynamic drivingforce for lithium uptake into the particles.

Ion exchange particles are removed continuously from the first stirredtank reactor as a slurry into a buffer tank and loaded in batches into asmall stirred tank reactor (2406) for washing to remove residual brine.Then, the particles are transferred in batches to another small stirredtank reactor (2405) for elution with 1.0 N sulfuric acid to producelithium sulfate solution, which is drained out of the compartment andout of the bottom of the tank. Then the particles are transferred toanother small stirred tank reactor (2404) for washing to remove residualacid. Then the particles are transferred to a buffer tank, from wherethey are fed continuously into the first large stirred tank reactor torepeat the cycle.

The lithium sulfate is concentrated through reverse osmosis andpurified. Then, the lithium sulfate solution is mixed with a solution ofsodium carbonate to precipitate lithium carbonate.

Example 15 Lithium Extraction Using Switched Network of Stirred TankReactors

Lithium is extracted from a brine using a stirred tank reactor loadedwith a fluidized bed of ion exchange particles. The brine is a naturalchloride solution containing approximately 300 ppm Li, 80,000 ppm Na,1,000 ppm Ca, and 3,000 ppm Mg. The ion exchange particles are comprisedof a Li₄Mn₅O₁₂ material coated with polystyrene The ion exchangeparticles contain 95 wt. % Li₄Mn₅O₁₂ and 5 wt. % polystyrene. Theparticles are approximately spherical with a mean diameter of 50microns.

The ion exchange particles are loaded into a network of six stirred tankreactors, which form a switched network (FIG. 20). Each stirred tankreactor comprises a large tank, an overhead stirrer, a pH probe, a pipefor adding base into the tank, and a compartment that contains the ionexchange particles with a porous polymer support. The porous polymersupports are formed with a bilayer structure with a coarse polypropylenemesh (500 micron pores) and a fine polyether ether ketone mesh (20micron pores). The porous polymer support divides the bottom of thetanks from the top of the tanks, contains the ion exchange particles inthe top of the tanks, and allows fluid to drain out of the tanks throughthe mesh and into pipes connected at the bottoms of the tanks. In eachtank, the compartment represents about 99% of the volume of the tank.

In each stirred tank reactor, the particles are sequentially stirredwith brine, water, 0.75 N sulfuric acid, and again with water. When theparticles are stirred with brine, the particles absorb lithium from thebrine while releasing protons into the brine. As protons are released,the pH of the brine drops. The pH probe measures the change in pH andtriggers base to be added to the brine through the pipe. This baseneutralizes the protons released from the particles and maintains astrong thermodynamic driving force for lithium uptake into theparticles. The brine is drained from the compartment through the porousmesh and from the tank out a pipe in the bottom while leaving the ionexchange particles in the compartment. The particles are then washedwith water three times to remove residual brine, and each time the wateris drained from the bottom of the tank. Then, the particles are elutedwith the sulfuric acid, and the particles release lithium to form alithium sulfate solution while absorbing protons. Then, the lithiumsulfate solution is drained from the bottom of the tank. Then, theparticles are washed again to remove residual acid. Then, the particlesare returned to a brine step and the cycle repeats. This cycle functionsto extract lithium from the brine and produce a lithium sulfatesolution.

The network of stirred tank reactors is operated is batch mode with thereactors switching so that at any given time, one reactor is beingeluted with acid (2501), one reactor is being washed with water toremove residual acid (2502), three reactors are being treated with brineto absorb lithium into the particles (2503, 2504, 2505), and one reactoris being washed with water to remove residual brine (2506).

The lithium sulfate is concentrated through reverse osmosis, purified,and electrolyzed to form a lithium hydroxide solution. The lithiumhydroxide solution is crystallized to form a lithium hydroxide powder.

While preferred embodiments of the present invention have been shown anddescribed herein, it will be obvious to those skilled in the art thatsuch embodiments are provided by way of example only. Numerousvariations, changes, and substitutions will now occur to those skilledin the art without departing from the invention. It should be understoodthat various alternatives to the embodiments of the invention describedherein is optionally employed in practicing the invention. It isintended that the following claims define the scope of the invention andthat methods and structures within the scope of these claims and theirequivalents be covered thereby.

1.-53. (canceled)
 54. A process for the extraction of lithium ions froma liquid resource, comprising: a. contacting an ion exchange materialwith the liquid resource; and b. increasing the pH of the liquidresource before contact with the ion exchange material, during contactwith the ion exchange material, after contact with the ion exchangematerial and combinations thereof.
 55. The process of claim 54, whereinthe ion exchange material is loaded into one or more compartments in atank.
 56. The process of claim 55, wherein the process further comprisesmoving the liquid resource through the one or more compartments in thetank.
 57. The process of claim 55, wherein the tank comprises injectionports.
 58. The process of claim 57, wherein the process furthercomprises using the injection ports to increase the pH of the liquidresource before contact with the ion exchange material, during contactwith the ion exchange material, after contact with the ion exchangematerial, or combinations thereof.
 59. (canceled)
 60. (canceled) 61.(canceled)
 62. The process of claim 54, wherein the ion exchangematerial comprises a plurality of ion exchange particles.
 63. Theprocess according to claim 62, wherein the plurality of ion exchangeparticles in the ion exchange material is selected from uncoated ionexchange particles, coated ion exchange particles and combinationsthereof.
 64. The process of claim 54, wherein the ion exchange materialis a porous ion exchange material.
 65. The process of claim 64, whereinthe porous ion exchange material comprises a network of pores thatallows liquids to move quickly from the surface of the porous ionexchange material to the plurality of ion exchange particles.
 66. Theprocess of claim 64, wherein the porous ion exchange material is in theform of porous ion exchange beads.
 67. The process of claim 63, whereincoated ion exchange particles comprise an ion exchange material and acoating material.
 68. The process of claim 67, wherein the coatingmaterial of the coated ion exchange particles comprises a carbide, anitride, an oxide, a phosphate, a fluoride, a polymer, carbon, acarbonaceous material, or combinations thereof.
 69. The process of claim67, wherein the coating material of the coated ion exchange particles isselected from the group consisting of TiO₂, ZrO₂, MoO₂, SnO₂, Nb₂O₅,Ta₂O₅, SiO₂, Li₂TiO₃, Li₂ZrO₃, Li₂SiO₃, Li₂MnO₃, Li₂MoO₃, LiNbO₃,LiTaO₃, AlPO₄, LaPO₄, ZrP₂O₇, MoP₂O₇, Mo₂P₃O₁₂, BaSO₄, AlF₃, SiC, TiC,ZrC, Si₃N₄, ZrN, BN, carbon, graphitic carbon, amorphous carbon, hardcarbon, diamond-like carbon, solid solutions thereof, and combinationsthereof.
 70. The process of claim 67, wherein the coating material ofthe coated ion exchange particles is selected from the group consistingof polyvinyl fluoride, polyvinylidene difluoride, polyvinyl chloride,polyvinylidene dichloride, polyethylene, polypropylene, polyphenylenesulfide, polytetrafluoroethylene, polytetrofluoroethylene, sulfonatedpolytetrofluoroethylene, polystyrene, polydivinylbenzene, polybutadiene,sulfonated polymer, carboxylated polymer,tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acidcopolymer, copolymers and combinations thereof.
 71. The process of claim67, wherein the ion exchange material of the coated ion exchangeparticles is selected from the group consisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂,Li₂TiO₃, Li₂MnO₃, Li₂SnO₃, LiMn₂O₄, Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂,LiTiO₂, Li₄TiO₄, Li₇Ti₁₁O₂₄, Li₃VO₄, Li₂Si₃O₇, LiFePO₄, LiMnPO₄,Li₂CuP₂O₇, Al(OH)₃, LiCl.xAl(OH)₃.yH₂O, SnO₂.xSb₂O₅.yH₂O,TiO₂.xSb₂O₅.yH₂O, solid solutions thereof, and combinations thereof;wherein xis from 0.1-10; and y is from 0.1-10.
 72. The process of claim63, wherein the uncoated ion exchange particles comprise an ion exchangematerial.
 73. The process of claim 72, wherein the ion exchange materialof the uncoated ion exchange particles is selected from the groupconsisting of Li₄Mn₅O₁₂, Li₄Ti₅O₁₂, Li₂TiO₃, Li₂MnO₃, Li₂SnO₃, LiMn₂O₄,Li_(1.6)Mn_(1.6)O₄, LiAlO₂, LiCuO₂, LiTiO₂, Li₄TiO₄, Li₇Ti₁₁O₂₄, Li₃VO₄,Li₂Si₃O₇, LiFePO₄, LiMnPO₄, Li₂CuP₂O₇, Al(OH)₃, LiCl.xAl(OH)₃.yH₂O,SnO₂.xSb₂O₅.yH₂O, TiO₂.xSb₂O₅.yH₂O, solid solutions thereof, andcombinations thereof; wherein xis from 0.1-10; and y is from 0.1-10. 74.The process of claim 54, wherein the pH of the liquid resource isincreased to an ideal pH range for the extraction of lithium ions fromthe liquid resource, wherein the ideal pH range is from 6 to
 9. 75. Theprocess of claim 54, wherein the pH of the liquid resource is increasedwhen the pH of the liquid resource is less than about 6 before contactwith the ion exchange material, during contact with the ion exchangematerial, after contact with the ion exchange material and combinationsthereof.
 76. The process of claim 75, wherein the pH of the liquidresource is increased by adding base to raise the pH of the liquidresource to from about 6 to about 9.